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At least 613 records · Page 34

All sources NASA NTRS DOE OSTI

DOE OSTI2013

Crystal structures and phase transitions in Sr doped Ba{sub 2}InTaO{sub 6} perovskites

The crystal structures of the double perovskites of the type Ba{sub 2−x}Sr{sub x}InTaO{sub 6} have been studied by synchrotron X-ray and neutron powder diffraction methods. The structures are based on ordered array of the tilted InO{sub 6} and TaO{sub 6} octahedra, with the Ba/Sr cations being completely disordered. The structure evolves from cubic to monoclinic Fm3{sup ¯}m→{sup x∼0.6}I4/m→{sup x∼1.2}I2/m→{sup x∼1.6}P2{sub 1}/n. The changes in the symmetry induced by replacing the Ba with Sr have been identified by a symmetry-mode analysis. Variable temperature S-XRD studies of selected examples have shown that heating the samples induces the same sequence of transitions observed in the composition dependent studies. - Graphical abstract: The evolution of the structure of the B-site ordered perovskites has been determined by high resolution powder diffraction. The nature of the transitions are probed by examination of the symmetry-adapted modes. Display Omitted - Highlights: • Synthesis of Ba{sub 2−x}Sr{sub x}InTaO{sub 6} cation ordered perovskites. • Synchrotron X-ray and neutron diffraction structural studies of Ba{sub 2−x}Sr{sub x}InTaO{sub 6}. • Phase transitions in Ba{sub 2−x}Sr{sub x}InTaO{sub 6}. • Symmetry-adapted mode analysis of phase transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Effect of gamma radiation on the photocatalytic properties of Cu doped titania nanoparticles

Highlights: • Defective Cu doped TiO{sub 2} powders were prepared by sol-gel route and gamma treatment. • Nanoscale analysis show evidence of internal doping by Cu{sup 2+} in the TiO{sub 2} sublattice. • Catalyst surfaces defect sites improve significantly the photocatalytic efficiency. • (Cu{sup 2+}, V{sub O}{sup -}) cooperative effects promote the photoelectrochemical properties of TiO{sub 2}. - Abstract: The aim of this paper is to study the effect of gamma-rays on structural, physicochemical, optical and photocatalytic performance of TiO{sub 2} nanoparticles doped with different concentrations of copper ranging from 0 to 6 at.%. The powders have been prepared by sol-gel technique and annealed at 400 °C. They were irradiated by gamma-rays with doses varying from 14 to 60 KGy. These investigations confirm the formation of anatase TiO{sub 2} nanoparticles and Cu{sup 2+} ion substitution for Ti{sup 4+} sites within the TiO{sub 2} structure. This study also shows that, once the TiO{sub 2} structure is saturated with copper, a metallic copper segregation is formed at the crystallite surfaces. After gamma irradiation, samples present a crystalline core and a disordered shell structure as a result of the formation of oxygen vacancies. Such oxygen vacancies at the TiO{sub 2} nanocrystal surface lead to a remarkable enhancement of the photocatalytic activity of Cu-doped TiO{sub 2} catalysts.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2013

Ti{sub 5}O{sub 5} superstructures of cubic titanium monoxide

A cubic model is proposed for the Ti{sub 5}O{sub 5} (Ti{sub 5}▪O{sub 5}□ ≡ Ti{sub 90}▪{sub 18}O{sub 90}□{sub 18}) superstructure of nonstoichiometric titanium monoxide Ti{sub x}O{sub z} with double imperfection. The unit cell of the cubic Ti{sub 5}O{sub 5} superstructure has the threefold lattice parameter of the unit cell of the basis disordered B1 structure of Ti{sub x}O{sub z} monoxide and belongs to space group <##> } P m } 3 }¯ m $ Pm/bar 3m $ Pm 3-bar m </##>. The channel of the disorder-order transition, i.e., Ti{sub x}O{sub z} (space group <##> } F m } 3 }¯ m $ Fm/bar 3m $ Fm 3-bar m </##>)-Ti{sub 5}O{sub 5} (space group <##> } P m } 3 }¯ m $ Pm/bar 3m $ Pm 3-bar m </##>), includes 75 superstructure vectors of seven stars {k_1_0}, {k_7}, {k_6_(_1_)}, {k_6_(_2_)}, {k_4_(_1_)}, {k_4_(_2_)}, and {k_1}. The distribution functions of Ti and O atoms over the sites of the cubic Ti{sub 5}O{sub 5} superstructure are calculated. A comparison of the X-ray and electron diffraction data obtained for ordered TiO{sub 1.087} monoxide with the theoretical simulation results supports the existence of the cubic Ti{sub 5}O{sub 5} superstructure. The cubic (space group <##> } P m } 3 }¯ m $ Pm/bar 3m $ Pm 3-bar m </##>) Ti{sub 5}O{sub 5} superstructure is shown to be a high-temperature structure relative to the well-known monoclinic (space group C2/m) superstructure of the same type.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2017

Monte Carlo simulations of disorder in ZnSn N 2 and the effects on the electronic structure

In multinary compound semiconductors, cation disorder can decisively alter the electronic properties and impact potential applications. ZnSnN 2 is a ternary nitride of interest for photovoltaics, which forms in a wurtzite-derived crystal structure. In the ground state, every N anion is coordinated by two Zn and two Sn cations, thereby observing the octet rule locally. Using a motif-based model Hamiltonian, we performed Monte Carlo simulations that provide atomistic representations of ZnSnN 2 with varying degrees of cation disorder. Subsequent electronic structure calculations describe the evolution of band gaps, optical properties, and carrier localization effects as a function of the disorder. We find that octet-rule conserving disorder is practically impossible to avoid but perfectly benign, with hardly any effects on the electronic structure. In contrast, a fully random cation distribution would be very detrimental, but fortunately it is energetically highly unfavorable. A degree of disorder that can realistically be expected for nonequilibrium thin-film deposition leads to a moderate band-gap reduction and to moderate carrier localization effects. Comparing the simulated structures with experimental samples grown by sputtering, we find evidence that these samples indeed incorporate a certain degree of octet-rule violating disorder, which is reflected in the x-ray diffraction and in the optical absorption spectra. This study demonstrates that the electronic properties of ZnSnN 2 are dominated by changes of the local coordination environments rather than long-range ordering effects.

14 SOLAR ENERGY↗

DOE OSTI2025

Using Multiple Isotope-Labeled Infrared Spectra for the Structural Characterization of an Intrinsically Disordered Peptide

Intrinsically disordered proteins (IDPs) rapidly interconvert between conformers, requiring an ensemble description. This complicates their experimental characterization, and force field limitations pose challenges for their simulation. Here, in this work, we use isotope-labeled and unlabeled infrared (IR) spectra to reweight simulated ensembles of the elastin-like peptide GVGVPGVG, a paradigmatic disordered peptide. By comparing the results obtained with different spectra, we explicitly show that the weights are underdetermined by the ensemble averaged data. We identify which labels and frequency regions maximize structural information while minimizing sensitivity to simulation error and show that these regions report on whether the peptide makes specific interactions. Our work shows the importance of incorporating simulations and simulated spectra at the planning stages of isotope-labeled IR experiments and more generally provides a framework for interpreting IR data for IDPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Shape-memory alloy micro-actuator

A method of producing an integral piece of thermo-sensitive material, which is responsive to a shift in temperature from below to above a phase transformation temperature range to alter the material's condition to a shape-memory condition and move from one position to another. The method is characterized by depositing a thin film of shape-memory material, such as Nickel titanium (Ni-Ti) onto a substrate by vacuum deposition process such that the alloy exhibits an amorphous non-crystalline structure. The coated substrate is then annealed in a vacuum or in the presence of an inert atmosphere at a selected temperature, time and cool down rate to produce an ordered, partially disordered or fully disordered BCC structure such that the alloy undergoes thermoelastic, martinsetic phase transformation in response to alteration in temperature to pass from a martinsetic phase when at a temperature below a phase transformation range and capable of a high level of recoverable strain to a parent austenitic phase in a memory shape when at a temperature above the phase transformation range. Also disclosed are actuator devices employing shape-memory material actuators that deform from a set shape toward an original shape when subjected to a critical temperature level after having been initially deformed from the original shape into the set shape while at a lower temperature. The actuators are mechanically coupled to one or more movable elements such that the temperature-induce deformation of the actuators exerts a force or generates a motion of the mechanical element(s).

Busch, John D.↗

DOE OSTI2021

Influence of Polymorphs and Local Defect Structures on NMR Parameters of Graphite Fluorides

In this study, the role of local molecular structure on calculated 13 C and 19 F NMR chemical shifts for graphite fluoride materials was explored by using gauge-including projector augmented wave (GIPAW) computational methods for different periodic crystal polymorphs and density functional theory (DFT) gauge-including atomic orbital (GIAO) computational methods for individual graphite fluoride platelets, i.e., fluorinated graphene (FG). The impact of stacking sequences, d -spacing, and ring conformations on fully fluorinated graphite fluoride structures was investigated. A range of different defects including Stone–Wales, F and C vacancies, void formation, and F inversion were also evaluated using FG structures. These calculations show that distinct chemical shift signatures exist for many of these polymorphs and defects, therefore providing a basis for spectral assignment and development of models describing the mean local CF structure in disordered graphite fluoride materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

The electrochemical storage mechanism in oxy-hydroxyfluorinated anatase for sodium-ion batteries

Replacing lithium ions with sodium ions as the charge carriers in rechargeable batteries can induce noticeable differences in the electrochemical storage mechanisms of electrode materials. Many material parameters, such as particle size, morphology, and the presence of defects, are known to further affect the storage mechanism. Here, we report an investigation of how the introduction of titanium vacancies into anatase TiO 2 affects the sodium storage mechanism. From pair distribution function analysis, we observe that sodium ions are inserted into titanium vacancies at the early stage of the discharge process. This is supported by density functional theory calculations, which predict that sodium insertion is more favourable at vacancies than at interstitial sites. Our calculations also show that the intercalation voltage is sensitive to the anion coordination environment of the vacancy. Sodiation to higher concentrations induces a phase transition toward a disordered rhombohedral structure, similar to that observed in defect-free TiO 2 . Finally, we find that the X-ray diffraction pattern of the rhombohedral phase drastically changes depending on the composition and degree of disorder, providing further comprehension on the sodium storage mechanism of anatase.

25 ENERGY STORAGE↗

DOE OSTI2015

Fast ion conductivity in strained defect-fluorite structure created by ion tracks in Gd 2 Ti 2 O 7

The structure and ion-conducting properties of the defect-fluorite ring structure formed around amorphous ion-tracks by swift heavy ion irradiation of Gd 2 Ti 2 O 7 pyrochlore are investigated. High angle annular dark field imaging complemented with ion-track molecular dynamics simulations show that the atoms in the ring structure are disordered, and have relatively larger cation-cation interspacing than in the bulk pyrochlore, illustrating the presence of tensile strain in the ring region. Density functional theory calculations show that the non-equilibrium defect-fluorite structure can be stabilized by tensile strain. The pyrochlore to defect-fluorite structure transformation in the ring region is predicted to be induced by recrystallization during a melt-quench process and stabilized by tensile strain. Static pair-potential calculations show that planar tensile strain lowers oxygen vacancy migration barriers in pyrochlores, in agreement with recent studies on fluorite and perovskite materials. Lastly, in view of these results, it is suggested that strain engineering could be simultaneously used to stabilize the defect-fluorite structure and gain control over its high ion-conducting properties.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Pb-Apatite Framework as a Generator of Novel Flat-Band CuO-Based Physics

Based upon density functional theory (DFT) calculations, we present the basic electronic structure of CuPb 9 (PO 4 ) 6 O (Cu-doped lead apatite, aka LK-99), in two scenarios: (1) where the structure is constrained to the P3 symmetry and (2) where no symmetry is imposed. At the DFT level, the former is predicted to be metallic while the latter is found to be a charge-transfer insulator. In both cases the filling of these states is nominally d 9 , consistent with the standard Cu 2+ valence state, and Cu with a local magnetic moment of order 0.7 μ B . In the metallic case we find these states to be unusually flat (∼0.2 eV dispersion), giving a very high density of electronic states (DOS) at the Fermi level that we argue can be a host for novel electronic physics. The flatness of the bands is the likely origin of symmetry-lowering gapping possibilities that would remove the spectral weight from E F . Motivated by some initial experimental observations of metallic or semiconducting behavior, we propose that disorder (likely structural) is responsible for closing the gap. Here, we consider a variety of possibilities that could possibly close the charge-transfer gap but limit consideration to kinds of disorder that preserve electron count. Of the possible kinds we considered (spin disorder, O populating vacancy sites, and Cu on less energetically favorable Pb sites), the local Cu moment, and consequently the charge-transfer gap, remains robust. We conclude that disorder responsible for metallic behavior entails some kind of doping where the electron count changes. Further, we claim that the emergence of the flat bands should be due to weak wave function overlap between the orbitals on Cu and O sites, owing to the directional character of the constituent orbitals. Therefore, finding an appropriate host structure for minimizing hybridization between Cu and O while allowing them to still weakly interact should be a promising route for generating flat bands at E F which can lead to interesting electronic phenomena, regardless of whether LK-99 is a superconductor.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Heteroepitaxial Integration of ZnGeN 2 on GaN Buffers Using Molecular Beam Epitaxy

Recently theorized hybrid II-IV-N 2 /III-N heterostructures, based on current commercialized (In,Ga)N devices, are predicted to significantly advance the design space of highly efficient optoelectronics in the visible spectrum, yet there are few epitaxial studies of II-IV-N 2 materials. In this work, we present heteroepitaxial ZnGeN 2 grown on GaN buffers and AlN templates. We demonstrate that a GaN nucleating surface is crucial for increasing the ZnGeN 2 crystallization rate to combat Zn desorption, extending the stoichiometric growth window from 215 degrees C on AlN to 500 degrees C on GaN buffers. Structural characterization reveals well-crystallized films with threading dislocations extending from the GaN buffer. These films have a critical thickness for relaxation of 20-25 nm as determined by reflection high energy electron diffraction (RHEED) and cross-sectional scanning electron microscopy (SEM). The films exhibit a cation-disordered wurtzite structure, with lattice constants a = 3.216 +/- 0.004 A and c = 5.215 +/- 0.005 A determined by RHEED and X-ray diffraction (XRD). This work demonstrates a significant step toward the development of hybrid ZnGeN 2 -GaN integrated devices.

36 MATERIALS SCIENCE↗

DOE OSTI2016

The order-disorder transition in Cu{sub 2}ZnSnS{sub 4} – A neutron scattering investigation

In this work a series of stoichiometric Cu{sub 2}ZnSnS{sub 4} (CZTS) samples annealed at different temperatures in the range of 473–623 K were investigated. The temperature dependence of the Cu/Zn-order-disorder behavior was analyzed by neutron powder diffraction measurements. Cu fully occupies the 2a and Sn the 2b position within the whole temperature range. For Zn and the remaining Cu on sites 2d and 2c, a clear change from ordered to disordered kesterite structure is found. The critical temperature T{sub c} for this Landau-type second order transition was determined as 552±2 K. It was found that in Cu{sub 2}ZnSnS{sub 4} very long annealing times are necessary to reach equilibrium at low temperatures. - Graphical abstract: The order-disorder transition in Cu{sub 2}ZnSnS{sub 4} was investigated using neutron diffraction techniques on samples annealed in the temperature range of 473–623 K. The critical temperature T{sub c} for this Landau-type second order transition was determined as 552±2 K. Display Omitted - Highlights: • The order-disorder transformation of Cu{sub 2}ZnSnS{sub 4} follows a Landau‐type behavior for a second order transition. • The critical exponent β is 0.57±0.06. • The critical temperature was determined as 552±2 K. • A fully ordered (within the standard deviation) Cu{sub 2}ZnSnS{sub 4} sample was synthesized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Effect of chemical order on the magnetic and electronic properties of epitaxial off-stoichiometry F e x S i 1 - x thin films

Off-stoichiometry, epitaxial Fe x Si 1-x thin films (0.5 < x < 1.0) exhibit D0 3 or B2 chemical order, even far from stoichiometry. Theoretical calculations show the magnetic moment is strongly enhanced in the fully chemically disordered A2 phase, while both theoretical and experimental results show that the magnetization is nearly the same in the B2 and D0 3 phases, meaning partial chemical disorder does not influence the magnetism. The dependencies of the magnetic moments are directly and nonlinearly linked to the number of Si atoms, primarily nearest neighbor but also to a lesser extent (up to 10%) next nearest neighbor, surrounding Fe, explaining the similarities between B2 and D0 3 and the strong enhancement for the A2 structure. The calculated electronic density of states shows many similarities in both structure and spin polarization between the D0 3 and B2 structures, while the A2 structure exhibits disorder broadening and a reduced spin polarization.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Spectroscopic investigations on oxidized multi-walled carbon nanotubes

The pristine multi-walled carbon nanotubes (MWCNTs) were oxidized by the ultrasonication process. The oxidized MWCNTs were characterized by the X-ray diffraction (XRD), ultraviolet–visible (UV-Vis) and Fourier transform -Raman (FT-Raman) spectroscopic techniques. The XRD analysis confirms that the oxidized MWCNTs exist in a hexagonal structure and the sharp XRD peak corresponds to the (002) Bragg’s reflection plane, which indicates that the MWCNTs have higher crystalline nature. The UV-Vis analysis confirms that the MWCNTs functionalized with the carboxylic acid. The red shift was observed corresponds to the D band in the Raman spectrum, which reveals that the reduced disordered graphitic structure of oxidized MWCNTs. The strong Raman peak was observed at 2563 cm{sup -1} corresponds to the overtone of the D band, which is the characteristic vibrational mode of oxidized MWCNTs. The carboxylic acid functionalization of MWCNTs enhances the dispersibility, which paves the way for potential applications in the field of biosensors and targeted drug delivery.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2022

Oxygen Deficiency and Migration-Mediated Electric Polarization in Magnetic Fe,Co-Substituted SrTiO3−δ

We use density functional theory (DFT) calculations to show that oxygen vacancies (vO) and mobility induce noncentrosymmetric polar structures in SrTi1−x−yFexCoyO3−δ (STFC, x=y=0.125) with δ={0.125,0.25}, enhance the saturation magnetization, and give rise to large changes in the electric polarization |ΔP|. We present an intuitive set of rules to describe the properties of STFC, which are based on the interplay between (Co/Fe)-vO defects, magnetic cation coordination, and topological vacancy disorder. STFC structures consist of layered crystals with sheets of linearly organized O4,5,6-coordinated Fe–Co pairs, sandwiched with layers of O5-coordinated Ti. (Co/Fe)-vO defects are the source of crystal distortions, cation off-centering and bending of the oxygen octahedra which, considering the charge redistribution mediated by vO and the cations’ electronegativity and valence states, triggers an effective electric polarization. Oxygen migration for δ=0.125 leads to |ΔP|>∼10 µC/cm2 due to quantum-of-polarization differences between δ=0.125 structures. Increasing the oxygen deficiency to δ=0.25 yields |ΔP|, the O migration of which resolved polarization for δ=0.25 is >∼3 µC/cm2. Magnetism is dominated by the Fe,Co spin states for δ=0.125, and there is a contribution from Ti magnetic moments (∼1 μB) for δ=0.25. Magnetic and electric order parameters change for variations of δ or oxygen migration for a given oxygen deficiency. Our results capture characteristics observed in the end members of the series SrTi(Co,Fe)O3, and suggest the existence of a broader set of rules for oxygen-deficient multiferroic oxides.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Orientation-dependent mutual crystalline and amorphous order in a single phase solid

Amorphous materials distinguish themselves from crystalline materials by lacking long-range order while retaining structural order at the local scale (2–5 Å). However, the complexity in topological and chemical order prevents current characterization tools from fully unveiling the structure in disordered materials. Consequently, the nature of medium-range order in amorphous materials has remained elusive. The Zachariasen and crystal competing models have been proposed to describe disordered phases and have both been verified through synthesis and characterization. The main difference between them is thought to be whether the amorphous phase shows medium-range order. Here we demonstrate a form of organized inorganic matter that is amorphous in two dimensions, while exhibiting long-range order and a high degree of crystallinity in the third. The structure consists of periodically stacked 2-dimensional amorphous Nb-W-O monolayers without long-range in-plane order. The unique periodic and therefore crystalline stacking along one principal axis enables direct imaging and revealed that the amorphous Nb-W-O monolayers formed in agreement with the Zachariasen model for 2 dimensions. Our findings show that the gap between crystalline and amorphous materials does not only depend on medium-range order but can also apply to principal dimensions within the same solid.

Nanowires↗

DOE OSTI2022

Local structure and ion storage properties of vanadate cathode materials regulated by the pre-alkalization

Aqueous Zn-ion batteries using mild acidic electrolytes utilizing a Zn 2+ /H + dual-ion storage mechanism have shown great potential in achieving high energy density comparable to non-aqueous lithium-ion batteries. Here, this study reveals that hydrated alkali-ions regulate the formation of alkali-intercalated vanadate layered compounds. Among various vanadate materials, lithium-intercalated vanadate has the largest interlayer spacing and most disordered local structure, exhibiting the largest storage capacity of 308 mA h g –1 at 0.05 A g –1 for Zn 2+ /H + dual-ion storage and improved charge transfer and transport kinetics and cycling performance, evidenced by in situ X-ray diffraction and ex situ X-ray total scattering and pair distribution function analysis. Our study provides new insight into designing layered vanadate materials for high-capacity aqueous batteries.

25 ENERGY STORAGE↗

DOE OSTI2019

Reduction Mechanism of Iron Oxide Briquettes by Carbonaceous Materials Extracted from Blast Furnace Dust

The reducibility of carbonaceous powder extracted from blast furnace dust was investigated. In this study, pickling treatment was used for BF bag dust and BF gravitational dust to extract the carbonaceous material. The structural characteristics of carbonaceous material were studied by X-ray diffraction, scanning electron microscope, and energy-dispersive spectrometer. The reduction of ferric oxide and carbon gasification experiments were researched by thermogravimetry. The results show that the pickled raw coal gives the highest reducibility, which is followed by BF bag dust and BF gravitational dust. The reason for this is that the higher disordered crystalline structure leads to stronger gasification reactivity, and further results in stronger reduction reactivity. Based on the randomized nucleation model, the kinetic analysis shows that the activation energies for the reduction reaction of BF gravitational dust, BF bag dust, and raw coal after pickling are 300.14, 180.43, and 124.62 kJ mol{sup −1}, respectively.

36 MATERIALS SCIENCE↗