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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 1,513 records · Page 84
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Complex defect chemistry of hydrothermally-synthesized Nb-substituted β$'$-LiVOPO 4

Lithium vanadyl phosphate (LiVOPO 4 ) is a next-generation multielectron battery cathode that can intercalate up to two Li-ions per V-ion through the redox couples of V 4+ /V 3+ and V 5+ /V 4+ . However, its rate capacity is undermined by the sluggish Li-ion diffusion in the high-voltage region (4 V for V 5+ /V 4+ redox). Nb substitution was used to expand the crystal lattice to facilitate Li-ion diffusion. Here, in this work, Nb substitution was achieved via hydrothermal synthesis, which resulted in a new, lower symmetry β'-LiVOPO 4 phase with preferential Nb occupation of one of the two V sites. This phase presents complex defect chemistries, including cation vacancies and hydrogen interstitials, characterized by a combination of X-ray and neutron diffraction, elemental and thermogravimetric analyses, X-ray absorption spectroscopy, and magnetic susceptibility measurements. The Nb-substituted samples demonstrated improved capacity retention and rate capabilities in the high-voltage region, albeit an enlarged voltage hysteresis related to a partial V 4+ /V 3+ redox reaction, as evidenced by ex situ X-ray absorption spectroscopy and pair distribution function analysis. This work highlights the importance of understanding the complex defect chemistry and its consequence on electrochemistry in polyanionic intercalation compounds.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effect of growth dynamics on the structural, photophysical and pseudocapacitance properties of famatinite copper antimony sulphide colloidal nanostructures (including nanosheets)

Facile phase selective synthesis of copper antimony sulphide (CAS) nanostructures is important because of their tunable photoconductive and electrochemical properties. In this study, off-stoichiometric famatinite phase CAS (fCAS) quasi-spherical and quasi-hexagonal colloidal nanostructures (including nanosheets) of sizes, 2.4–18.0 nm were grown under variable conditions of temperature (60–200 °C), time and oleylamine capping ligand concentration using copper(II) acetylacetonate and antimony(III) diethyldithiocarbamate precursors. Data from powder X-ray diffraction, Raman spectroscopy and high-resolution scanning/transmission electron microscopy confirm the tetragonal structure of the famatinite phase. X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy data suggest a correlation of particle size, morphology and composition of the off-stoichiometric fCAS nanostructures with growth temperature and time, and oleylamine concentration. The off-stoichiometric Cu 3-a Sb 1+b S 4±c (a, b, c – mole fractions) nanostructures being severely copper-deficient and antimony-rich, exhibit shallow-lying acceptor copper vacancy states, deep-lying donor states of antimony interstitials, sulphur vacancies and antimony-copper antisites and shallow-lying acceptor surface trapping states. Further, these electronic states are likely implicated in tunable UV-visible absorption and bandgaps between 2.3 and 2.8 eV, and broad visible-NIR photoluminescence with fast recombination of radiative lifetimes between 0.2 and 6.2 ns, confirmed from absorption, steady-state and time-resolved photoluminescence spectroscopies. Additionally, cyclic voltammetry and electrochemical impedance spectroscopy confirm that electrodes of the fCAS nanostructures display slightly variable pseudocapacitance of charge-storage primarily via possible sodium ion intercalation with a high specific capacitance of ~84 F g -1 obtained at a scan rate of 5 mV s -1 . Overall, these results show the influence of composition, in particular point defects, phase quality and morphology on the optical and pseudocapacitance properties of fCAS nanostructures, suitable as solar absorbers or electrodes for energy storage devices.

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

Aluminosilicate colloidal gels: from the early age to the precipitation of zeolites

Aluminosilicate hydrogels are often considered to be precursors for the crystallisation of zeolites carried out under hydrothermal conditions. The preparation of mechanically homogeneous aluminosilicate gels enables the study of these materials through bulk rheology and observation of the aging dynamics until the precipitation of crystalline zeolites. The first part of this study deals with the establishment of ternary state diagrams, in order to identify the range of chemical formulations that enable preparation of single-phase homogeneous gels. Then, by studying the viscoelastic moduli during the gelation reaction, and by yielding the gel under large deformation, we propose an empirical law considering the partial order of reaction on each chemical element, to predict the gelation time according to the chemical formulation. The scaling behavior of the elastic properties of this colloidal gel shows a transition from a strong link behavior to a weak link regime. Long term aging results in the shrinkage of the gel, accompanied by syneresis of interstitial liquid at the surface. Zeolites precipitate through crystallisation by a particle attachment mechanism, when thermodynamic equilibrium is reached. The stoichiometry of the precipitated zeolites is not only consistent with the concentration of the remaining species in the supernatant but, surprisingly, it is also very close to the partial order of the reaction of the chemical elements involved in the determination of the critical gel point. This indicates a strong correlation between the morphology of the soft amorphous gel network that is formed at an early age and those of the final solid precipitated crystals.

36 MATERIALS SCIENCE↗
DOE OSTI2012

A thermal porosimetry method to estimate pore size distribution in highly porous insulating materials

Standard pore size determination methods such as mercury porosimetry, nitrogen sorption, microscopy, or x-ray tomography are not always applicable to highly porous, low density, and thus very fragile materials. For this kind of materials, a method based on thermal characterization is proposed. Indeed, the thermal conductivity of a highly porous and insulating medium is significantly dependent on the thermal conductivity of the interstitial gas that depends on both gas pressure and size of the considered pore (Knudsen effect). It is also possible to link the pore size with the thermal conductivity of the medium. Thermal conductivity measurements are realized on specimens placed in an enclosure where the air pressure is successively set to different values varying from 10{sup -1} to 10{sup 5} Pa. Knowing the global porosity ratio, an effective thermal conductivity model for a two-phase air-solid material based on a combined serial-parallel model is established. Pore size distribution can be identified by minimizing the sum of the quadratic differences between measured values and modeled ones. The results of the estimation process are the volume fractions of the chosen ranges of pore size. In order to validate the method, measurements done on insulating materials are presented. The results are discussed and show that pore size distribution estimated by the proposed method is coherent.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Hydrogen diffusion in lead zirconate titanate and barium titanate

Hydrogen is a potential clean-burning, next-generation fuel for vehicle and stationary power. Unfortunately, hydrogen is also well known to have serious materials compatibility issues in metals, polymers, and ceramics. Piezoelectric actuator materials proposed for low-cost, high efficiency high-pressure hydrogen internal combustion engines (HICE) are known to degrade rapidly in hydrogen. This limits their potential use and poses challenges for HICE. Hydrogen-induced degradation of piezoelectrics is also an issue for low-pressure hydrogen passivation in ferroelectric random access memory. Currently, there is a lack of data in the literature on hydrogen species diffusion in piezoelectrics in the temperature range appropriate for the HICE as charged via a gaseous route. We present 1 HNMR quantification of the local hydrogen species diffusion within lead zirconate titanate and barium titanate on samples charged by exposure to high-pressure gaseous hydrogen ~32 MPa. We discuss results in the context of theoretically predicted interstitial hydrogen lattice sites and aqueous charging experiments from existing literature.

barium titanate↗
DOE OSTI2013

Quantum chemical elucidation of the mechanism for hydrogenation of TiO{sub 2} anatase crystals

Hydrogenation of TiO{sub 2} is relevant to hydrogen storage and water splitting. We have carried out a detailed mechanistic study on TiO{sub 2} hydrogenation through H and/or H{sub 2} diffusion from the surface into subsurface layers of anatase TiO{sub 2} (101) by periodic density functional theory calculations implementing on-site Coulomb interactions (DFT + U). Both H atoms and H{sub 2} molecules can migrate from the crystal surface into TiO{sub 2} near subsurface layer with 27.8 and 46.2 kcal/mol energy barriers, respectively. The controlling step for the former process is the dissociative adsorption of H{sub 2} on the surface which requires 47.8 kcal/mol of energy barrier. Both hydrogen incorporation processes are expected to be equally favorable. The barrier energy for H{sub 2} migration from the first layer of the subsurface O{sub sub1} to the 2nd layer of the subsurface oxygen O{sub sub2} requires only 6.6 kcal. The presence of H atoms on the surface and inside the subsurface layer tends to promote both H and H{sub 2} penetration into the subsurface layer by reducing their energy barriers, as well as to prevent the escape of the H{sub 2} from the cage by increasing its escaping barrier energy. The H{sub 2} molecule inside a cage can readily dissociate and form 2HO-species exothermically ({Delta}H =-31.0 kcal/mol) with only 26.2 kcal/mol barrier. The 2HO-species within the cage may further transform into H{sub 2}O with a 22.0 kcal/mol barrier and 19.3 kcal/mol exothermicity relative to the caged H{sub 2} molecule. H{sub 2}O formation following the breaking of Ti-O bonds within the cage may result in the formation of O-vacancies and surface disordering as observed experimentally under a high pressure and moderately high temperature condition. According to density of states analysis, the projected density of states of the interstitial H, H{sub 2}, and H{sub 2}O appear prominently within the TiO{sub 2} band gap; in addition, the former induces a shift of the band gap position notably towards the conduction band. The thermochemistry for formation of the most stable sub-surface species (2HO and H{sub 2}O) has been predicted. These results satisfactorily account for the photo-catalytic activity enhancement observed experimentally by hydrogenation at high temperatures and high pressures.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Cascaded emission of linearly polarized single photons from positioned InP/GaInP quantum dots

We report on the optical characterization of site-controlled InP/GaInP quantum dots (QDs). Spatially resolved low temperature cathodoluminescence proves the long-range ordering of the buried emitters, revealing a yield of ∼90% of optically active, positioned QDs and a strong suppression of emitters on interstitial positions. The emission of single QDs shows a pronounced degree of linear polarization along the [0,−1,1] crystal axis with an average degree of polarization of 94%. Photon correlation measurements of the emission from a single QD indicate the single-photon character of the exciton and biexciton emission lines as well as the cascaded nature of the photon pair.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

Dynamics of iron-acceptor-pair formation in co-doped silicon

The pairing dynamics of interstitial iron and dopants in silicon co-doped with phosphorous and several acceptor types are presented. The classical picture of iron-acceptor pairing dynamics is expanded to include the thermalization of iron between different dopants. The thermalization is quantitatively described using Boltzmann statistics and different iron-acceptor binding energies. The proper understanding of the pairing dynamics of iron in co-doped silicon will provide additional information on the electronic properties of iron-acceptor pairs and may become an analytical method to quantify and differentiate acceptors in co-doped silicon.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Formation of magnetic discontinuities through superposition of force-free magnetic fields: Periodic boundaries

In ideal magnetohydrodynamics characterized by an infinite electrical conductivity, the magnetic flux across an arbitrary fluid surface is conserved in time. The magnetofluid then can be partitioned into contiguous subvolumes of fluid, each of which entraps its own subsystem of magnetic flux. During dynamical evolution of the magnetofluid, these subvolumes press into each other; and in the process, two such subvolumes may come into direct contact while ejecting a third interstitial subvolume. Depending on the orientations of magnetic fields of the two interacting subvolumes, the magnetic field at the common surface of interaction may become discontinuous and a current sheet is formed there. This process of current sheet formation and their subsequent decay is believed to be a plausible mechanism for coronal heating and may also be responsible for various eruptive phenomena at the solar corona. In this work, we explore this theoretical concept through numerical simulations of a viscous, incompressible magnetofluid characterized by infinite electrical conductivity. In particular, we show that if the initial magnetic field is prescribed by superposition of two linear force-free fields with different torsion coefficients, then formation of current sheets are numerically realizable in the neighborhood of magnetic nulls.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Study of microstructure and semiconductor to metallic conductivity transition in solid state sintered Li{sub 0.5}Mn{sub 0.5}Fe{sub 2}O{sub 4−δ} spinel ferrite

Li{sub 0.5}Mn{sub 0.5}Fe{sub 2}O{sub 4} ferrite has been prepared by solid state sintering route. XRD pattern showed single phased cubic spinel structure. The samples exhibited typical character of plastoferrite with ring shaped surface microstructure. New feature observed in the present ferrite is the frequency activated conductivity transition from semiconductor to metallic state above 800 K. The increase of conductivity with frequency in the semiconducting regime follows Jonscher power law, while decrease of conductivity in metallic regime obeys Drude equation. The conductivity in semiconductor regime has been understood by hopping mechanism of localized charge carriers among the cations in B sites of cubic spinel structure. At higher temperatures, overlapping of electronic orbitals from neighbouring ions and free particle like motion of lighter Li{sup +} ions among interstitial lattices contributed metallic conductivity. The samples provided evidence of localized nature of the charge carriers at lower temperatures and increasing delocalized character with the increase of measurement temperature. From application point of view, such ferrites behave as semiconductor at low temperature and allow electromagnetic wave to pass through, but transform into a metallic reflector with negative dielectric constant at high temperature.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Mn concentration dependent structural and optical properties of a-plane Zn{sub 0.99-x}Mn{sub x}Na{sub 0.01}O

Non-polar a-plane (112{sup ¯}0) Zn{sub 0.99−x}Mn{sub x}Na{sub 0.01}O (x = 0, 0.02, 0.03, 0.04, and 0.05) thin films have been prepared on r-plane (112{sup ¯}0) sapphire substrates by pulsed laser deposition (PLD). The influences of Mn content on the structural and optical properties of the films have been studied. It is indicated that moderate Mn doping facilitates the non-polar growth of ZnO, and all the doped films are single phase with a hexagonal wurtzite structure. The transmittance spectra suggested that all films are transparent in the visible region exhibiting a transmittance above 80%. Mn{sup 2+} doped Zn{sub 0.99}Na{sub 0.01}O shows an initial decrease of optical band gap (OBG) for small concentration of Mn, followed by a monotonic increase. The anomalous decrease in OBG for low concentrations of Mn is attributed to the strong exchange interaction present between the sp electrons of the host matrix and d electrons of Mn. Emission studies were also performed showing suppressed blue-shifted ultraviolet band and dominant violet-blue bands, which might originate from the zinc vacancy (V{sub Zn}) and zinc interstitial (Zn{sub i}) defects. The intensity of defect-related emission peaks is Mn doping-level-dependent as well and the results coincide well with that from the structural analyses.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Origins of low resistivity and Ge donor level in Ge ion-implanted ZnO bulk single crystals

The energy level of Ge in Ge-ion implanted ZnO single crystals is studied by Hall-effect and photoluminescence (PL) methods. The variations in resistivity from ∼10{sup 3} Ωcm for un-implanted samples to ∼10{sup −2} Ωcm for as-implanted ones are observed. The resistivity is further decreased to ∼10{sup −3} Ωcm by annealing. The origins of the low resistivity are attributed to both the zinc interstitial (Zn{sub i}) related defects and the electrical activated Ge donor. An activation energy of Ge donors estimated from the temperature dependence of carrier concentration is 102 meV. In PL studies, the new peak at 372 nm (3.33 eV) related to the Ge donor is observed in 1000 °C annealed samples.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Native defects in MBE-grown CdTe

Deep-level traps in both n- and p-type CdTe layers, grown by molecular-beam epitaxy on GaAs substrates, have been investigated by means of deep-level transient spectroscopy (DLTS). Four of the traps revealed in the DLTS spectra, which displayed exponential kinetics for capture of charge carriers into the trap states, have been assigned to native point defects: Cd interstitial, Cd vacancy, Te antisite defect and a complex formed of the Te antisite and Cd vacancy. Three further traps, displaying logarithmic capture kinetics, have been ascribed to electron states of treading dislocations generated at the mismatched interface with the substrate and propagated through the CdTe layer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

In-situ stress analysis with X-Ray diffraction for yield locus characterization of sheet metals

A main problem in the field of sheet metal characterization is the inhomogeneous plastic deformation in the gauge regions of specimens which causes the analytically calculated stresses to differ from the sought state of stress acting in the middle of the gauge region. To overcome this problem, application of X-Ray diffraction is analyzed. For that purpose a mobile X-ray diffractometer and an optical strain measurement system are mounted on a universal tensile testing machine. This enables the recording of the whole strain and stress history of a material point. The method is applied to uniaxial tension tests, plane strain tension tests and shear tests to characterize the interstitial free steel alloy DC06. The applicability of the concepts of stress factors is verified by uniaxial tension tests. The experimentally obtained values are compared with the theoretical values calculated with crystal elasticity models utilizing the orientation distribution functions (ODF). The relaxation problem is addressed which shows itself as drops in the stress values with the strain kept at a constant level. This drop is analyzed with elasto-viscoplastic material models to correct the measured stresses. Results show that the XRD is applicable to measure the stresses in sheet metals with preferred orientation. The obtained yield locus is expressed with the Yld2000–2D material model and an industry oriented workpiece is analyzed numerically. The comparison of the strain distribution on the workpiece verifies the identified material parameters.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Giant g-factors of natural impurities in synthetic quartz

We report the observation of g-factors of natural paramagnetic impurities in a pure synthetic quartz crystal at milli-Kelvin temperatures. Measurements are made by performing spectroscopy using multiple high-Q whispering gallery modes sustained in the crystal. Extreme sensitivity of the method at low temperatures allows the determination of natural residual impurities introduced during the crystal growth. We observe g-factors that significantly differ from integer multiples of the electron g-factor in vacuum, and with values of up to 7.6, which reveals much stronger coupling between impurities and the crystal lattice than in previous studies. Both substitutional and interstitial ions are proposed as candidates for the observed interactions.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Energetics of vacancy segregation to symmetric tilt grain boundaries in hexagonal closed pack materials

Molecular static simulations of 190 symmetric tilt grain boundaries in hexagonal closed pack metals were used to understand the energetics of vacancy segregation, which is important for designing stable interfaces in harsh environments. Simulation results show that the local arrangements of grain boundaries and the resulting structural units have a significant influence on the magnitude of vacancy binding energies, and the site-to-site variation within each boundary is substantial. Comparing the vacancy binding energies for each site in different c/a ratio materials shows that the binding energy increases significantly with an increase in c/a ratio. For example, in the [12{sup ¯}10] tilt axis, Ti and Zr with c/a = 1.5811 have a lower vacancy binding energy than the Mg with c/a = 1.6299. Furthermore, when the grain boundary energies of all 190 boundaries in all three elements are plotted against the vacancy binding energies of the same boundaries, a highly negative correlation (r = −0.7144) is revealed that has a linear fit with a proportionality constant of −25 Å{sup 2}. This is significant for applications where extreme environmental damage generates lattice defects and grain boundaries act as sinks for both vacancies and interstitial atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2014

High-cycle fatigue behavior of Ti-5Al-2.5Sn ELI alloy forging at low temperatures

High-cycle fatigue properties of Ti-5Al-2.5Sn Extra Low Interstitial (ELI) alloy forging were investigated at low temperatures. The high-cycle fatigue strength at low temperatures of this alloy was relatively low compared with that at ambient temperature. The crystallographic orientation of a facet formed at a fatigue crack initiation site was determined by electron backscatter diffraction (EBSD) method in scanning electron microscope (SEM) to understand the fatigue crack initiation mechanism and discuss on the low fatigue strength at low temperature. Furthermore, in terms of the practical use of this alloy, the effect of the stress ratio (or mean stress) on the high-cycle fatigue properties was evaluated using the modified Goodman diagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗