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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 1,657 records · Page 92
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Laminin receptor specific therapeutic gold nanoparticles (198AuNP-EGCg) show efficacy in treating prostate cancer

Systemic delivery of therapeutic agents to solid tumors is hindered by vascular and interstitial barriers. We hypothesized that prostate tumor specific epigallocatechingallate( EGCg) functionalized radioactive gold nanoparticles, when delivered intratumorally (IT), will circumvent transport barriers, resulting in targeted delivery of therapeutic payloads. The results described herein provide unequivocal validation of our hypothesis. We report the development of inherently therapeutic gold nanoparticles derived from Au-198 isotope; the range of 198Au β-particle ( ~ 11 mm in tissue or ~1100 cell diameters) is sufficiently long to provide cross-fire effects of radiation dose delivered to cells within the prostate gland and short enough to minimize radiation dose to critical tissues near the periphery of the capsule. The formulation of biocompatible 198AuNPs utilizes the redox chemistry of prostate tumor specific phytochemical EGCg as it converts gold salt into gold nanoparticles and also selectively binds with excellent affinity to Laminin67R receptors which are over expressed in prostate tumor cells. Pharmacokinetic studies in PC-3 xenograft SCID mice showed ~72% retention of 198AuNP-EGCg in tumors 24 h after intratumoral administration. Therapeutic studies showed 80% reduction of tumor volumes after 28 days demonstrating significant inhibition of tumor growth compared to controls. This innovative “green nanotechnological“approach serves as a basis for designing target specific antineoplastic agents. This novel intratumorally injectable 198AuNP-EGCg nanotherapeutic agent may provide significant advances in oncology for use as an effective treatment for prostate and other solid tumors.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2013

Mapping Strain-rate Dependent Dislocation-Defect Interactions by Atomistic Simulations

Probing the mechanisms of defect-defect interactions at strain rates lower than 106 s-1 is an unresolved challenge to date to molecular dynamics (MD) techniques. Here we propose a novel atomistic approach based on transition state theory and the concept of a strain-dependent effective activation barrier that is capable of simulating the kinetics of dislocation-defect interactions at virtually any strain rate, exemplified within 10-7 to 107 s-1. We apply this approach to the problem of an edge dislocation colliding with a cluster of self-interstitial atoms (SIA) under shear deformation. Using an activation-relaxation algorithm (1), we uncover a unique strain-rate dependent trigger mechanism that allows the SIA cluster to be absorbed during the process leading to dislocation climb. Guided by this finding, we determine the activation barrier of the trigger mechanism as a function of shear strain, and use that in a coarse-graining rate equation formulation for constructing a mechanism map in the phase space of strain-rate and temperature. Our predictions of a crossover from a defect recovery at the low strain rate regime to defect absorption behavior in the high strain-rate regime are validated against our own independent, direct MD simulations at 105 to 107 s-1. Implications of the present approach for probing molecular-level mechanisms in strain-rate regimes previously considered inaccessible to atomistic simulations are discussed.

activation mecanism↗
DOE OSTI2017

Active molecular iodine photochemistry in the Arctic

During springtime, the Arctic atmospheric boundary layer undergoes frequent rapid depletions in ozone and gaseous elemental mercury due to reactions with halogen atoms, influencing atmospheric composition and pollutant fate. Although bromine chemistry has been shown to initiate ozone depletion events, and it has long been hypothesized that iodine chemistry may contribute, no previous measurements of molecular iodine (I 2 ) have been reported in the Arctic. Iodine chemistry also contributes to atmospheric new particle formation and therefore cloud properties and radiative forcing. Here we present Arctic atmospheric I 2 and snowpack iodide (I - ) measurements, which were conducted near Utqiagvik, AK, in February 2014. Using chemical ionization mass spectrometry, I 2 was observed in the atmosphere at mole ratios of 0.3–1.0 ppt, and in the snowpack interstitial air at mole ratios up to 22 ppt under natural sunlit conditions and up to 35 ppt when the snowpack surface was artificially irradiated, suggesting a photochemical production mechanism. Further, snow meltwater I-measurements showed enrichments of up to ~1,900 times above the seawater ratio of I-/Na + , consistent with iodine activation and recycling. Modeling shows that observed I 2 levels are able to significantly increase ozone depletion rates, while also producing iodine monoxide (IO) at levels recently observed in the Arctic. Furthermore, these results emphasize the significance of iodine chemistry and the role of snowpack photochemistry in Arctic atmospheric composition, and imply that I 2 is likely a dominant source of iodine atoms in the Arctic.

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

Local structure of Sr 2 CuO 3.3 , a 95 K cuprate superconductor without CuO 2 planes

The local structure of the highly “overdoped” 95 K superconductor Sr 2 CuO 3.3 determined by Cu K X-ray absorption fine structure (XAFS) at 62 K in magnetically oriented samples shows that 1) the magnetization is perpendicular to the c axis; 2) at these levels of precision the Cu sublattice is tetragonal in agreement with the crystal structure; the O sublattice has 3) continuous -Cu-O- chains that orient perpendicular to an applied magnetic field; 4) approximately half-filled -Cu-O- chains that orient parallel to this field; 5) a substantial number of apical O vacancies; 6) O ions at some apical positions with expanded Cu-O distances; and 7) interstitial positions that imply highly displaced Sr ions. These results contradict the universally accepted features of cuprates that require intact CuO 2 planes, magnetization along the c axis, and a termination of the superconductivity when the excess charge on the CuO 2 Cu ions exceeds 0.27. These radical differences in charge and structure demonstrate that this compound constitutes a separate class of Cu-O–based superconductors in which the superconductivity originates in a different, more complicated structural unit than CuO 2 planes while retaining exceptionally high transition temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

From particle attachment to space-filling coral skeletons

Reef-building corals and their aragonite (CaCO 3 ) skeletons support entire reef ecosystems, yet their formation mechanism is poorly understood. Here we used synchrotron spectromicroscopy to observe the nanoscale mineralogy of fresh, forming skeletons from six species spanning all reef-forming coral morphologies: Branching, encrusting, massive, and table. In all species, hydrated and anhydrous amorphous calcium carbonate nanoparticles were precursors for skeletal growth, as previously observed in a single species. The amorphous precursors here were observed in tissue, between tissue and skeleton, and at growth fronts of the skeleton, within a low-density nano- or microporous layer varying in thickness from 7 to 20 µm. Brunauer-Emmett-Teller measurements, however, indicated that the mature skeletons at the microscale were space-filling, comparable to single crystals of geologic aragonite. Nanoparticles alone can never fill space completely, thus ion-by-ion filling must be invoked to fill interstitial pores. Such ion-by-ion diffusion and attachment may occur from the supersaturated calcifying fluid known to exist in corals, or from a dense liquid precursor, observed in synthetic systems but never in biogenic ones. Concomitant particle attachment and ion-by-ion filling was previously observed in synthetic calcite rhombohedra, but never in aragonite pseudohexagonal prisms, synthetic or biogenic, as observed here. Models for biomineral growth, isotope incorporation, and coral skeletons’ resilience to ocean warming and acidification must take into account the dual formation mechanism, including particle attachment and ion-by-ion space filling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Cation reordering instead of phase transitions: Origins and implications of contrasting lithiation mechanisms in 1D ζ- and 2D α-V 2 O 5

Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (V 2 O 5 ) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-V 2 O 5 that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-V 2 O 5 crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, operando synchrotron X-ray diffraction measurements, and phase-field modeling. We find the operation of sharply divergent mechanisms to accommodate increasing concentrations of Li-ions: a series of distortive phase transformations that result in puckering and expansion of interlayer spacing in layered α-V 2 O 5 , as compared with cation reordering along interstitial sites in tunnel-structured ζ-V 2 O 5 . By alleviating distortive phase transformations, the ζ-V 2 O 5 cathode shows reduced voltage hysteresis, increased Li-ion diffusivity, alleviation of stress gradients, and improved capacity retention. The findings demonstrate that alternative lithiation mechanisms can be accessed in metastable compounds by dint of their reconfigured atomic connectivity and can unlock substantially improved electrochemical performance not accessible in the thermodynamically stable phase.

25 ENERGY STORAGE↗
DOE OSTI2023

Chemical interactions that govern the structures of metals

Most metals adopt simple structures such as body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed (HCP) structures in specific groupings across the periodic table, and many undergo transitions to surprisingly complex structures on compression, not expected from conventional free-electron-based theories of metals. First-principles calculations have been able to reproduce many observed structures and transitions, but a unified, predictive theory that underlies this behavior is not yet in hand. Discovered by analyzing the electronic properties of metals in various lattices over a broad range of sizes and geometries, a remarkably simple theory shows that the stability of metal structures is governed by electrons occupying local interstitial orbitals and their strong chemical interactions. The theory provides a basis for understanding and predicting structures in solid compounds and alloys over a broad range of conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Intermediate range order in supercooled water

The temperature dependence of the heights of the first and second x-ray diffraction peaks in supercooled water measured down to 244 K are found to display very different behaviours. While the first peak intensity remains essentially constant, the second peak increases strongly with decreasing temperature. In real space this is concomitant with the reduction of the number of non-bonded interstitial molecules between the first and second shells. It is found that although the first O-O shell in supercooled water is unchanged upon supercooling, the variations in intermediate range order are mainly associated with the growth of a predominantly tetrahedral network that is distinctly different from ice-Ih. Moreover, in this temperature regime we find a direct correlation between the height of the second diffraction peak and the intensity changes in the 2nd, 3rd, 4th and 5th peaks in the oxygen-oxygen pair distribution function.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Performance of pumped counterflow virtual impactors to study aerosol interactions with laboratory generated warm clouds

Pumped Counterflow Virtual Impactors (PCVI) are designed to separate aerosols based on aerodynamic diameter, which is particularly useful for isolating cloud droplets and ice crystals from smaller particles. However, the PCVI transmission efficiency (TE) values reported in the literature show considerable variability, and little information is available on the TEs for cloud liquid droplets. Here, we determined the optimal flow conditions for PCVI sampling for different activation ratios from the MTU Pi-cloud chamber, highlighting the conditions that maximize droplet residual sampling while minimizing interstitial transmission. Even for a lower limit cloud activation ratio = 1:10, an add flow of 1.5 LPM achieves a residual fraction greater than 0.80, with a droplet TE of ∼15% for typical Pi-Chamber droplets with diameters between 3.5 to 10 µm. This framework can be adapted for field cloud measurements based on the cloud conditions of interest. TE for cloud droplets under flow conditions at which ∼99% of the unactivated submicron particles were removed was substantially lower between 8 and 16% than for supermicron dry particles (∼30 to 40% for 3 µm polystyrene latex spheres). In addition, we conducted a comparison of the performances of three similar PCVI units to assess repeatability for dry aerosols and cloud droplets. All three PCVIs performed similarly in rejecting submicron particles smaller than the desired cutoff diameter. One of the units showed lower TEs due to a misalignment of the internal orifice. We discuss a procedure that improved alignment and performance.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Dynamic Void Growth and Shrinkage in Mg under Electron Irradiation

We report in-situ atomic-scale investigation of void evolution, including growth, coalescence and shrinkage, under electron irradiation. With increasing irradiation dose, the total volume of voids increased linearly, while nucleation rate of new voids decreased slightly, and the total number of voids decreased. Some voids continued to grow while others shrank to disappear, depending on the nature of their interactions with nearby self-interstitial loops. For the first time, surface diffusion of adatoms was observed largely responsible for the void coalescence and thickening. These findings provide fundamental understanding to help with the design and modeling of irradiation-resistant materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Dose dependence of radiation damage in nano-structured amorphous SiOC/crystalline Fe composite

Here, through examination of radiation tolerance properties of amorphous silicon oxycarbide (SiOC) and crystalline Fe composite to averaged damage levels, from approximately 8 to 30 displacements per atom (dpa), we demonstrated that the Fe/SiOC interface and the Fe/amorphous Fe x Si y O z interface act as efficient defect sinks and promote the recombination of vacancies and interstitials. For thick Fe/SiOC multilayers, a clear Fe/SiOC interface remained and no irradiation-induced mixing was observed even after 32 dpa. For thin Fe/SiOC multilayers, an amorphous Fe x Si y O z intermixed layer was observed to form at 8 dpa, but no further layer growth was observed for higher dpa levels.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ionic-Liquid-Gating Induced Protonation and Superconductivity in FeSe, FeSe 0.93 S 0.07 , ZrNCl, 1 T -TaS 2 and Bi 2 Se 3 *

We report protonation in several compounds by an ionic-liquid-gating method, under optimized gating conditions. This leads to single superconducting phases for several compounds. Non-volatility of protons allows post-gating magnetization and transport measurements. The superconducting transition temperature T c is enhanced to 43.5 K for FeSe 0.93 S 0.07 , and 41 K for FeSe after protonation. Superconducting transitions with T c ~ 15 K for ZrNCl, ~7.2 K for 1T-TaS 2 , and ~3.8 K for Bi 2 Se 3 are induced after protonation. Electric transport in protonated FeSe 0.93 S 0.07 confirms high-temperature superconductivity. Our 1 H nuclear magnetic resonance (NMR) measurements on protonated FeSe 1- x S x reveal enhanced spin-lattice relaxation rate 1/ 1 T 1 with increasing x , which is consistent with the LDA calculations that H + is located in the interstitial sites close to the anions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Evidence of incomplete annealing at 800 °C and the effects of 120 °C baking on the crystal orientation and the surface superconducting properties of cold-worked and chemically polished Nb

High-purity niobium rods were cold-worked by wire-drawing, followed by various combinations of chemical polishing and high-vacuum baking at 120 °C or annealing at 800 °C in order to better understand changes to the surface superconducting properties resulting from typical superconducting radio-frequency cavity processing. AC susceptibility measurements revealed an enhanced upper transition T c at ~ 9.3–9.4 K in all samples that was stable through all annealing steps, a value significantly above the accepted T c of 9.23 K for pure annealed niobium. Corresponding elevations were seen in the critical fields, the ratio of the surface critical field H c3 to the bulk upper critical field H c2 rising to 2.3, well above the Ginzburg–Landau value of 1.695. Orientation imaging revealed an extensive dislocation rich sub-grain structure in the as-drawn rods, a small reduction of the surface strain after baking at 120 °C, and a substantial but incomplete recrystallization near the surface after annealing at 800 °C. We interpret these changes in surface superconducting and structural properties to extensive changes in the near-surface interstitial contamination produced by baking and annealing and to synergistic interactions between H and surface O introduced during electropolishing and buffered chemical polishing.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Ab initio study of H, He, Li and Be impurity effect in tungsten Σ3{112} and Σ27{552} grain boundaries

Density functional theory calculations were performed to study the effects of H, He, Li and Be on the cohesion of W Σ3<110>{112} and Σ27<110>{552} grain boundaries (GBs). In Σ3, Li causes the strongest embrittlement, while in Σ27 it is He. In both GBs, H slightly reduces the cohesion. Compared to He and Li, H exhibits much stronger attractive binding with W that may inhibit subsequent segregation of Li and He to the GBs. In Σ3, Be decreases the cohesion. However, in Σ27, Be strengthens the cohesion in several interstitial positions by increasing the bonding across the interface or by inducing GB restructuring.

Ab Initio↗
DOE OSTI2014

Searching for high magnetization density in bulk Fe: the new metastable Fe-6 phase

We report the discovery of a new allotrope of iron by first principles calculations. This phase has Pmn2(1) symmetry, a six-atom unit cell (hence the name Fe-6), and the highest magnetization density (M-s) among all the known crystalline phases of iron. Obtained from the structural optimizations of the Fe3C-cementite crystal upon carbon removal, Pmn2(1) Fe-6 is shown to result from the stabilization of a ferromagnetic FCC phase, further strained along the Bain path. Although metastable from 0 to 50 GPa, the new phase is more stable at low pressures than the other well-known HCP and FCC allotropes and smoothly transforms into the FCC phase under compression. If stabilized to room temperature, for example, by interstitial impurities, Fe-6 could become the basis material for high M-s rare-earth-free permament magnets and high-impact applications such as light-weight electric engine rotors or high-density recording media. The new phase could also be key to explaining the enigmatic high M-s of Fe16N2, which is currently attracting intense research activity.

Umemoto, K↗
DOE OSTI2015

Structure and properties of electronic and hole centers in CsBr from theoretical calculations

The electronic structure, geometry, diffusion barriers and optical properties of fundamental defects of CsBr are calculated using hybrid functional DFT and TD- DFT methods. The B3LYP functional with a modified exchange contribution has been used in an embedded cluster scheme to model the structure and spectroscopic properties of self-trapped triplet exciton, interstitial Br atoms and ions, self-trapped holes and Br vacancies. The calculated migration barriers and positions of maxima of optical absorption bands are in good agreement with experiment, justifying the obtained defect geometries. The o*-center triplet exciton luminescence energy is also accurately calculated.

Halliday, Matthew T.↗
DOE OSTI2015

Thermodynamic approach to the stability of multi-phase systems. Application to the Y 2 O 3 –Fe system

Oxide-metal systems (OMSs) are important in many practical applications, and therefore, are under extensive studies using a wide range of techniques. The most accurate theoretical approaches are based on density functional theory (DFT), which are limited to ~10 2 atoms. Multi-scale approaches, e.g., DFT+Monte Carlo, are often used to model OMSs at the atomic level. These approaches can describe qualitatively the kinetics of some processes but not the overall stability of OMSs. In this paper, we propose a thermodynamic approach to study equilibrium in multiphase systems, which can be sequentially enhanced by considering different defects and microstructures. We estimate the thermodynamic equilibrium by minimization the free energy of the whole multiphase system using a limited set of defects and microstructural objects for which the properties are calculated by DFT. As an example, we consider Y 2 O 3 +bcc Fe with vacancies in both the Y 2 O 3 and bcc Fe phases, Y substitutions and O interstitials in Fe, Fe impurities and antisite defects in Y 2 O 3 . The output of these calculations is the thermal equilibrium concentration of all the defects for a particular temperature and composition. The results obtained confirmed the high temperature stability of yttria in iron. As a result, model development towards more accurate calculations is discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗