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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 955 records · Page 53
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Polymorphic Metastability in Colloidal Semiconductor Nanocrystals

Metastable polymorphs of inorganic solids often possess material properties not present in the corresponding thermodynamic polymorphs, making them targets for the development of new functional materials. In contrast with isolating metastable bulk materials, syntheses of metastable polymorphs on the nanoscale are aided by fast non-equilibrium reaction kinetics and the favorable thermodynamic influence of surface energies, giving rise to greater ease of access to metastable high-temperature polymorphs and, in some cases, new polymorphs that do not exist in the bulk. The syntheses of metastable semiconductor nanocrystals are of interest for their potentially unique optoelectronic and physicochemical properties. However, in many material systems, synthesizing nanocrystalline products away from thermodynamic equilibrium in a predictable manner remains an outstanding challenge. This review outlines direct synthetic methodologies that have been developed to enable control over the nucleation and growth of metastable polymorphs of semiconductor nanocrystals by tailoring reaction conditions, precursor kinetics, ligand and surface effects, and other synthetic levers. The case studies reviewed herein expound on the direct syntheses of metastable ZnSe, Cu 2 SnSe 3 , CuInSe 2 , Ag 2 Se, and AgInSe 2 nanocrystals, and although there remain numerous examples of metastable nanocrystal syntheses outside of these metal chalcogenide systems, the concepts discussed are of general utility to the field of metastable nanocrystal syntheses as a whole. Explicit examples in which new functional properties are afforded by metastable polymorphs of the aforementioned material systems are presented within the context of applications for solar cells, photonics, and optical sensing. Finally, the factors that affect the kinetic persistence of metastable nanocrystalline polymorphs are discussed at length for these material systems.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Scaling laws and stability of nano-sized defect clusters in niobium via atomistic simulations and statistical analysis

The predictions of scaling laws for the structure and properties of defect clusters are generally limited to small defect clusters in their ground-state configurations. We investigated the size and geometrical configuration dependence of nano-sized defect clusters in niobium (Nb) using molecular dynamics. We studied the structure and stability of large clusters of size up to fifty defects for vacancies and one hundred defects for interstitials, as well as the role of helium and metastable configurations on the stability of these clusters. We compared three different interatomic potentials in order to determine the relative stability of these clusters as a function of their size and geometrical configurations. Additionally, we conducted a statistical analysis to predict the formation and binding energies of interstitial clusters as a function of both their size and configuration. We find that the size dependence of vacancy and interstitial clusters can be approximated by functional forms that account for bulk and surface effects as well as some considerations of elastic interactions. We also find that helium and metastable configurations can make vacancy and interstitial clusters thermally stable depending on the configuration. Our parameterized functional forms for the formation and binding energies are valid for a very broad range of defect sizes and configurations making it possible to be used directly in a coarse-grained modeling strategy such as Monte Carlo, cluster dynamics or dislocation dynamics which look at defect accumulation and evolution in microstructures.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modification of the Structure and Magnetic Properties of Cobalt-Doped Ferrihydrite Nanoparticles Under Heat Treatment

Nanoparticles of antiferromagnetic materials acquire the magnetic moment due to the surface effects and structural defects. According to the Neel hypothesis, magnetic moment μ{sub P} of a particle containing N magnetically active atoms with magnetic moment J can be estimated as μ{sub P} ∼ J · N{sup n} or μ{sub P} ∼ V{sup n}, where V is the particle volume. Numerous studies of the magnetic properties of ferrihydrite 5Fe{sub 2}O{sub 3}⋅9H{sub 2}O and ferritin revealed a value of n ≈ 1/2 for this material, in which Fe atoms have the octahedral surrounding of anions. We investigate the effect of low-temperature annealing of cobalt-doped ferrihydrite nanoparticles on their average size and magnetic properties. Using the Mössbauer spectroscopy study, we demonstrate that doping with Co makes Fe atoms enter the anion tetrahedra which leads to an increase in the exponent n〉1/2 in the expression μ{sub P} ∼ J · N{sup n}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Bacterial Ferrihydrite Nanoparticles: Preparation, Magnetic Properties, and Application in Medicine

Nanoparticles of antiferromagnetically ordered materials acquire the uncompensated magnetic moment caused by defects and surface effects. A bright example of such a nano-antiferromagnet is nanoferrihydrite consisting of particles 2–5 nm in size, the magnetic moment of which amounts to hundreds of Bohr magnetons per particle. We present a brief review of the studies on magnetic properties of ferrihydrite produced by bacteria. Special attention is focused on the aspects of possible biomedical applications of this material, i.e., the particle elimination, toxicity, and possible use for targeted drug delivery.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

A Review of Local-to-Nonlocal Coupling Methods in Nonlocal Diffusion and Nonlocal Mechanics

Local-to-nonlocal (LtN) coupling refers to a class of methods aimed at combining nonlocal and local modeling descriptions of a given system into a unified coupled representation. This allows to consolidate the accuracy of nonlocal models with the computational expediency of their local counterparts, while often simultaneously removing nonlocal modeling issues such as surface effects. The number and variety of proposed LtN coupling approaches have significantly grown in recent years, yet the field of LtN coupling continues to grow and still has open challenges. This review provides an overview of the state of the art of LtN coupling in the context of nonlocal diffusion and nonlocal mechanics, specifically peridynamics. Furthermore, we present a classification of LtN coupling methods and discuss common features and challenges. The goal of this review is not to provide a preferred way to address LtN coupling but to present a broad perspective of the field, which would serve as guidance for practitioners in the selection of appropriate LtN coupling methods based on the characteristics and needs of the problem under consideration.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2017

Direct measurement of critical resolved shear stress of prismatic and basal slip in polycrystalline Ti using high energy X-ray diffraction microscopy

Knowledge of the critical resolved shear stress (CRSS) values of different slip modes is important for accurately modeling plastic deformation of hexagonal materials. Here, we demonstrate that CRSS can be directly measured with an in-situ high energy X-ray diffraction microscopy (HEDM) experiment. A commercially pure Ti tensile specimen was deformed up to 2.6% strain. In-situ far-field HEDM experiments were carried out to track the evolution of crystallographic orientations, centers of masses, and stress states of 1153 grains in a material volume of 1.1mm×1mm×1mm. Predominant prismatic slip was identified in 18 grains, where the orientation change occurred primarily by rotation around the c-axis during specimen deformation. By analyzing the resolved shear stress on individual slip systems, the estimated CRSS for prismatic slip is 96±18 MPa. Predominant basal slip was identified in 22 other grains, where the 2 orientation change occurred primarily by tilting the c-axis about an axis in the basal plane. The estimated CRSS for basal slip is 127±33 MPa. The ratio of CRSS basal /CRSS prismatic is in the range of 1.7-2.1. From indirect assessment, the CRSS for pyramidal < c+a > slip is likely greater than 240MPa. Lastly, grain size and free surface effects on the CRSS value in different grains are also examined.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

Nanochannel structures in W enhance radiation tolerance

Developing high performance plasma facing materials (PFMs) is one of the greatest challenges for fusion reactors, because PFMs face unprecedented harsh environments including high flux plasma exposure, fast neutron irradiation and large transmutation gas. Tungsten (W) is considered as one of the most promising PFMs. Rapid accumulation of helium (He) atoms in such environments can lead to the He bubbles nucleation and even the formation of nano- to micro-scale “fuzz” on W surface, which greatly degrade the properties of W itself. The possible ejection of large W particulates into the core plasma can cause plasma instabilities. In this paper, we present a new strategy to address the root causes of bubble nucleation and “fuzz” formation by concurrently releasing He outside of W matrix through the nano-engineered channel structure (nanochannels). Comparing to ordinary bulk W, nanochannel W films with high surface-to-volume ratios are found to not only delay the growth of He bubbles, but also suppress the formation of “fuzz” (less than a half of the “fuzz” thickness formation in bulk W). Finally, molecular dynamic (MD) simulation results elucidate that low vacancy formation energy and high He binding energy in the nanochannel surface effectively help He release and affect He clusters distribution in W during He ion irradiation.

"fuzz"↗
DOE OSTI2025

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Upcycling linear low-density polyethylene waste to turbostratic graphene for high mass loading supercapacitors

Linear low-density polyethylene (LLDPE) waste is difficult to upcycle into more valuable carbon materials because it tends to completely decompose into small molecules during thermal processing. In this work, LLDPE is upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K 2 CO 3 ) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400–950°C without decomposition of the polymer feedstock. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800m 2 g -1 and average Raman I D /I G and I 2D /I G ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses a specific capacitance up to 175Fg -1 at a mass loading of 20mgcm -2 , which is two times the commercial requirement, yielding an areal capacitance of 3.5 Fcm -2 . Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8 % after 100,000 cycles at a current density of 4.0 Ag -1 . Additionally, the KCl and K 2 CO 3 solids are recycled and reused over 3 complete reaction cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling waste LLDPE and other varieties of polyethylene into a higher value graphene used for electrochemical energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Mechanism of ion pairing–induced co-ion penetration into the stern layer

In classical electric double layer (EDL) theory, co-ions—ions carrying the same charge as the electrode—are assumed to be excluded from the Stern layer because of electrostatic repulsion. However, ion pairing with adsorbed counterions may enable co-ions to access the EDL, a phenomenon that remains underexplored. Key questions therefore remain unresolved, including how deeply co-ions penetrate, how ion-specific properties govern them, and how ion pairing within the EDL differs from bulk solution. Here, in this study, we employ molecular dynamics simulations combined with well-tempered metadynamics to quantify co-ion penetration and ion-pairing thermodynamics at positively charged Mg-Al layered double hydroxide interfaces (σ = +20.6 μC/cm 2 ) in aqueous chloride electrolytes across 0.005–3 M range. We reveal a concentration-driven crossover: at dilute conditions, counterion–co-ion contact ion pairing (CIP) is thermodynamically unfavorable or only weakly favorable (ΔG CIP = +0.12 kcal/mol for Li + to −0.42 kcal/mol for K + ), leading to co-ion exclusion. As concentration increases (≥0.5 M), enhanced screening reduces surface repulsion and stabilizes CIP thermodynamics (ΔG CIP = −0.89 kcal/mol for Li + to −1.05 kcal/mol for K + at 3 M), enabling monovalent co-ions to penetrate the Stern layer following the hydration hierarchy K + > Na + > Li + , while divalent co-ions (Mg 2+ , Ca 2+ ) remain in the diffuse layer, forming only solvent-separated pairs. Comparison with bulk solution shows interfacial ion pairing is suppressed at low concentrations but converges to bulk-like thermodynamics at high concentrations, indicating surface effects vanish under strong screening. These results establish a quantitative framework linking ion-pairing thermodynamics to co-ion penetration and providing strategies to design electrochemical interfaces.

Co-ion penetration↗
DOE OSTI2022

Atomistic thermodynamics and kinetics of dicalcium silicate dissolution

Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.

36 MATERIALS SCIENCE↗
DOE OSTI2018

An asymptotically compatible meshfree quadrature rule for nonlocal problems with applications to peridynamics

In this paper, we present a meshfree quadrature rule for compactly supported nonlocal integro-differential equations (IDEs) with radial kernels. We apply this rule to develop a meshfree discretization of a peridynamic solid mechanics model that requires no background mesh. Existing discretizations of peridynamic models have been shown to exhibit a lack of asymptotic compatibility to the corresponding linearly elastic local solution. By posing the quadrature rule as an equality constrained least squares problem, we obtain asymptotically compatible convergence by introducing polynomial reproduction constraints. Our approach naturally handles traction-free conditions, surface effects, and damage modeling for both static and dynamic problems. We demonstrate high-order convergence to the local theory by comparing to manufactured solutions and to cases with crack singularities for which an analytic solution is available. We verify the applicability of the approach to realistic problems by reproducing high-velocity impact results from the Kalthoff–Winkler experiments.

42 ENGINEERING↗
DOE OSTI2019

Density estimation techniques for multiscale coupling of kinetic models of the plasma material interface

In this work we analyze two classes of Density-Estimation techniques which can be used to consistently couple different kinetic models of the plasma-material interface, intended as the region of plasma immediately interacting with the first surface layers of a material wall. In particular, we handle the general problem of interfacing a continuum multi-species Vlasov-Poisson-BGK plasma model to discrete surface erosion models. The continuum model solves for the energy-angle distributions of the particles striking the surface, which are then driving the surface response. A modification to the classical Binary-Collision Approximation (BCA) method is here utilized as a prototype discrete model of the surface, to provide boundary conditions and impurity distributions representative of the material behavior during plasma irradiation. The numerical tests revealed the superior convergence properties of Gaussian Mixture Models over Kernel Density Estimation methods, with Gaussian Mixtures and Epanechnikov-KDEs both being up to two orders of magnitude faster than Gaussian-KDEs. The methodology here presented allows a self-consistent treatment of the plasma-material interface in magnetic fusion devices, including both the near-surface plasma (plasma sheath and presheath) in magnetized conditions, and surface effects such as sputtering, back-scattering, and ion implantation. The same coupling techniques can also be utilized for other discrete material models such as Molecular Dynamics.

42 ENGINEERING↗
DOE OSTI2020

A classical molecular dynamics simulation method for the formation of “dry” gels from boro-aluminosilicate glass structures

In contact with water, glass transforms into amorphous and porous structures called gels. A simulation method based on classical molecular dynamics is proposed here to mimic “dry” gels forming from initial oxide glass structures. Six glass compositions were investigated. Two behaviours were evidenced depending on the initial glass composition, and in particular on the quantity of elements removed. If a large quantity of soluble elements (B, Na) was removed, it induced an increase in the average pore size within the gels, and the time needed to stabilise the gel structure increased because more local atomic rearrangements occurred. The gel network displayed a higher proportion of Si-Q4 at the expense of Si-Q3 and a lower average ring size compared to the glass network, irrespective of the glass composition. Surface effects were also highlighted in the dry gels, such as the presence of 3-coordinated Al and a decrease in the average angle Si-O-Si and Al-O-Al. Our findings will be compared to both wet gels and experimental data in further studies, to help find the best procedure to simulate such structures.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Multi-probe microstructure tracking during heat treatment without an in-situ setup: Case studies on martensitic steel, dual phase steel and β-Ti alloy

In-situ scanning electron microscopy observations of the microstructure evolution during heat treatments are increasingly demanded due to the growing number of alloys with complex microstructures. Post-mortem characterization of the as-processed microstructures rarely provides sufficient insight on the exact route of the microstructure formation. On the other hand, in-situ SEM approaches are often limited due to the arising challenges upon using an in-situ heating setup, e.g. in (i) employing different detectors, (ii) preventing specimen surface degradation, or (iii) controlling and measuring the temperature precisely. Here, we explore and expand the capabilities of the “mid-way” solution by step-wise microstructure tracking, ex-situ, at selected steps of heat treatment. This approach circumvents the limitations above, as it involves an atmosphere and temperature well-controlled dilatometer, and high resolution microstructure characterization (using electron channeling contrast imaging, electron backscatter diffraction, atom probe tomography, etc.). We demonstrate the capabilities of this approach by focusing on three cases: (i) nano-scale carbide precipitation during low-temperature tempering of martensitic steels, (ii) formation of transformation-induced geometrically necessary dislocations in a dual-phase steel during intercritical annealing, and (iii) the partial recrystallization of a metastable β-Ti alloy. - Highlights: • A multi-probe method to track microstructures during heat treatment is developed. • It enables the analysis of various complex phenomena, even those at atomistic scale. • It circumvents some of the free surface effects of classical in-situ experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Perturbing the spin state and conduction of Fe (II) spin crossover complexes with TCNQ

In this study, we investigated modifications driven by 7,7,8,8-tetracyanoquinodimethane (TCNQ) to the spin state configuration of [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal and both spin state and electric conductivity of [Fe{H 2 B(pz) 2 } 2 (bipy)] and TCNQ mixtures. The Fe 2+ site in the [Fe(3-bpp) 2 ](TCNQ) 2 co-crystal has a sizable orbital moment. During X-ray absorption measurements, the iron ion is partially excited to the high spin state and strong surface effects are indicated. Mixing TCNQ with the [Fe{H 2 B(pz) 2 } 2 (bipy)] spin crossover complex leads to a molecular combination with increased conductivity and drift carrier lifetimes. [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ, grown using dimethylformamide (DMF), are to great extent locked mainly in the low spin (LS) state across a broad temperature range and exhibit drift carrier lifetimes approaching 0.5 s. When deposited onto a ferroelectric polyvinylidenefluoride-hexafluoropropylene thin film substrate, [Fe{H 2 B(pz) 2 } 2 (bipy)], shows enhanced transistor carrier mobility, likely associated with the increasing cationic character of [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films with TCNQ.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Underlying mechanism of structural transformation between GaSb and GaAs response to intense electronic excitation

Ion irradiation of semiconductors has emerged as a promising approach for fabricating self-organized nanosystems with high atomic precision, despite often being accompanied by undesirable phenomena. Exploring the mechanisms underlying structural transformations is crucial for assessing nanostructure array types under complex irradiation environments. By quantitatively calculating the thermodynamically driven processes and analyzing the impact of intrinsic structural parameters, distinct structural transformations in response to intense electronic excitation are systematically investigated in gallium antimonide (GaSb) and gallium arsenide (GaAs) systems. In high-energy regimes, the nanofibers layer of GaSb exhibits intriguing structural discrepancy, characterized by partial nanofibers with coherent boundaries, interspersed nanopores accompanied by antisite defects and Ga precipitates, distinguishing to a series of discontinuous latent tracks that emerged within cylindrical trajectories in GaAs. Furthermore, significant diffusion behaviors of the nanohillocks are discovered in GaAs, with higher average roughness than GaSb, driven by the gradient stress distribution influenced by the free-surface effects. The deposition energy for melting phase formation, Gibbs free energy, and Ga diffusion coefficients contribute to the distinctive structural features, evidencing relatively stable morphological configurations and higher irradiation resistance in GaAs. Consequently, special optoelectronic properties associated with structural discrepancies facilitate the design and optimization of material functionalities by irradiation technologies.

36 MATERIALS SCIENCE↗