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At least 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Hydrogen induced dislocation core reconstruction in bcc tungsten

Dislocation, playing a crucial role in the plastic deformation of metals, can be significantly affected by introducing solute elements. Hydrogen (H) embrittlement is one such example, while the underlying mechanism for H affected dislocation structural stability and mobility remains unclear and the role of H has been controversial. Here, using first-principles calculations, we demonstrate that the effect of H on screw dislocation in bcc tungsten (W) is H concentration-dependent, signified by a H-induced transition of SD core structure. At low concentrations of H segregation, dislocation maintains the intrinsic easy-core structure, and H atoms are attached to the “periphery” of dislocation to enhance dislocation motion. In contrast, at high H concentrations, dislocation transforms into a hard-core, metal hydride-like structure, as H atoms become the “body” of dislocation to significantly reduce the dislocation mobility in W. Further, such local easy-to-hard transition can also be induced by the other solutes, including helium, carbon, nitrogen and oxygen. Our work sheds new light on the H-dislocation interactions in bcc W, having broad implications in the interstitial solute-related phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Crucial role of Reg I from acinar-like cell cluster touching with islets (ATLANTIS) on mitogenesis of beta cells in EMC virus-induced diabetic mice

Recently, we reported the presence of distinct cell clusters named acinar-like cell clusters touching Langerhans islets with thin interstitial surrounding (ATLANTIS) in human pancreas. A morphological study in humans demonstrated that ATLANTIS and islet cell clusters are found together in the microenvironment enclosed by a common basement membrane, and ATLANTIS releases vesicles containing Regenerating gene protein (REG Iα) to islet cell clusters. We examined 1) the presence or absence of ATLANTIS in homozygous Reg I (mouse homologue of human REG Iα) deficient (Reg I{sup −/-}) and wild-type mice, and 2) the possible role of ATLANTIS in the regeneration of beta cell clusters after encephalomyocarditis (EMC) virus (D-variant) infection in Reg I{sup −/-} and wild-type mice. ATLANTIS was found in both wild-type and Reg I{sup −/-} mice. In both groups, mean blood glucose increased transiently to greater than 14.0 mmol/L at 5 days after EMC virus infection and recovered to baseline at 12 days. At 12 days after EMC virus infection, lower BrdU labeling indices were observed in islet beta cells of Reg I{sup −/-} mice compared to wild-type mice. Beta cell volume 12 days after EMC virus infection in Reg I{sup −/-} mice did not differ from that of wild-type mice. These results suggest that Reg I, which is released from ATLANTIS to islet beta cell clusters, has a crucial role in beta cell regeneration in EMC virus-induced diabetes. The presence of mechanism(s) other than that mediated by Reg I in beta cell restoration after destruction by EMC virus was also suggested.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Improved thermoelectric performance of α- and β- Cu 2 Se through suppression of hole density using extrinsic copper vacancies

Modulating Cu + ion disorder in Cu 2 Se can enable control over the polymorphism and the carrier density leading to enhanced thermoelectric properties for both α- and β-Cu 2 Se. Here we report that the incorporation of Cr 3+ into the Cu 2 Se crystal lattice facilitates the stabilization of α-Cu 2 Se at 300 K leading to a large (~140%) reduction in the carrier density both below and above the phase transition. This is attributed to the reduction in the density of intrinsic copper interstitials (Cu$^{•}_{i}$) within the Cu (2-δ-λ) (Cr$^{··}_{Cu}$)λ(V$^{'}_{Cu}$)δ(Cu$^{π}_{i}$) δ-2λ (h • ) δ-2λ Se crystal lattice. Such optimization of the carrier density led to a large (63%) increase in the thermopower and a drastic (46%) reduction in the total thermal conductivity for both α- and β-Cu 2 Se matrices. Consequently, a significant enhancement of the thermoelectric performance is observed in the entire temperature range from 300 K to 773 K. This results in high average ZT values for both α-Cu 2 Se (ZT ave = 0.60) and β-Cu 2 Se (ZT ave = 0.97), which paves the way for both near room temperature and high temperatures applications. Furthermore, this work provides a new approach to optimize the thermoelectric performance of Cu 2 Se-based materials by leveraging the interaction between mobile intrinsic Cu$^{·}_{i}$ and extrinsic V$^{'}_{Cu}$ to suppress the hole density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Improving the structural consistency of C-S-H solid solution thermodynamic models

Simple aqueous-solid solution models of C-S-H (calcium silicate hydrate) are widely used in studies of cement hydration and waste-cement interactions. Even without a clear structural/mechanistic basis, such thermodynamic models yield a good description of solubility data in [Ca]-C/S space, while only satisfactory in [Si]-C/S, H{sub 2}O-C/S, [Ca]-[Si] spaces and in the 0.1 < C/S < 0.8 range. Here, using a multi-site (sublattice) concept, the ideal solid solution model of C-S-H is revised to make it consistent with the Richardson-Groves structural model of C-S-H and with the modern interpretation of spectroscopic ({sup 29}Si MAS NMR) and solubility data. Consideration of two site substitutions, (1) coupled H{sub 2}OCa{sup 2+} for SiO{sub 2}H{sub 2}{sup 2+} replacement in bridging tetrahedral and adjacent interlayer sites, and (2) substitution of interstitial Ca(OH){sub 2} for a vacancy, leads to a new CSHQ model of (A,B) (C,D)X type composed of two tobermorite-like and two jennite-like end members. Because this ideal sublattice SS model cannot fit solubility data well at 0.8 < C/S < 1.1, a simpler CSH3T model is constructed from a polymeric TobH (CaO){sub 2}(SiO{sub 2}){sub 3}(H{sub 2}O){sub 5}, a dimeric T2C (CaO){sub 3}(SiO{sub 2}){sub 2}(H{sub 2}O){sub 5}, and an ordered pentameric T5C (CaO){sub 2.5}(SiO{sub 2}){sub 2.5}(H{sub 2}O){sub 5} tobermorite-like end members. This solid solution model, limited to the range 0.67 < C/S < 1.5, has a correct built-in dependence of the mean silicate chain length on C/S, yields quite realistic fits to the solubility data, and provides a basis for extensions with foreign cations whose sites in the defect-tobermorite structure of C-S-H are known. To account for C-S-H compositions with C/S > 1.5, CSHQ end members were downscaled to one tetrahedral site and used within the simple mixing model. Despite some loss of structural consistency, the solubility and mean silicate chain length data can be reproduced well with this downscaled CSHQ model, capable of temperature corrections and dependencies of density and water content in fully-hydrated C-S-H on C/S ratio. Most literature solubility data sets can be modeled at the cost of moderate adjustments of CSHQ end-member solubility products within 0.2 to 0.6 pK units.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Energetics and diffusional properties of He in BCC Mo: an empirical potential for molecular dynamics simulations

This paper presents an interatomic potential for modeling of He defects and bubbles in body-centered-cubic (BCC) Mo. We utilize three existing framework: the Finnis-Sinclair (FS) potential for Mo-Mo, the Effective-Medium-Theory (EMT) for He-Mo, and the Hartree-Fock-Dispersion (HFD) potential for He-He interactions. The energetics of He defects and the diffusivity of He interstitial givens by the present potential agree well with ab initio calculations and experimental measurements. Furthermore, in agreement with theoretical prediction, it is shown that the introduction of He gas suppresses the surface diffusivity of BCC Mo, which decays exponentially with increasing He pressure acting on the free surface. The decay constant, with is correlated with the characteristic interaction volume for He-Mo, is close to the atomic volume of BCC Mo. This suppression effect is important to understand the mobility of small gas bubbles.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Kinetic Activation-Relaxation Technique and Self-Evolving Atomistic Kinetic Monte Carlo: Comparison of on-the-fly kinetic Monte Carlo algorithms

Here, we present a comparison of the Kinetic Activation–Relaxation Technique (k-ART) and the Self-Evolving Atomistic Kinetic Monte Carlo (SEAKMC), two off-lattice, on-the-fly Kinetic Monte Carlo (KMC) techniques that were recently used to solve several materials science problems. We show that if the initial displacements are localized the dimer method and the Activation–Relaxation Technique nouveau provide similar performance. We also show that k-ART and SEAKMC, although based on different approximations, are in agreement with each other, as demonstrated by the examples of 50 vacancies in a 1950-atom Fe box and of interstitial loops in 16,000-atom boxes. Generally speaking, k-ART’s treatment of geometry and flickers is more flexible, e.g. it can handle amorphous systems, and rigorous than SEAKMC’s, while the later’s concept of active volumes permits a significant speedup of simulations for the systems under consideration and therefore allows investigations of processes requiring large systems that are not accessible if not localizing calculations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Hydrogen Localization and Cluster Formation in α-Zr from First-Principles Investigations

We report alpha-zirconium (α-Zr) is a hydrogen atom host material used in nuclear energy and semiconducting applications due to Zr's excellent properties such as corrosion resistance, low thermal neutrons cross-section, and thermodynamically favorable interstitial sequestering of H atoms. Herein we use density functional theory simulations to systematically analyze the initial stages of H insertion in the Zr matrix, and determine optimal hydrogen localization, distribution, and clustering tendencies from a thermodynamics and kinetics perspective. Our results suggest that H occupation of tetrahedral sites is strongly favored, consistent with previous experimental and theoretical studies. Further, a cooperative effect in H localization is shown where H atoms favor clustering. The H pair is found to be the most stable by occupying tetrahedral sites with pairs at second nearest-neighbor positions (TTn2). Among the four H atom clusters, the most favorable configuration has two TTn2 pairs forming "box " or "zig-zag" shaped-cluster with the pairs separated by 3.03 or 3.25 Å, respectively. Nudged elastic band simulations suggest that the formation of TTn2 is facile and is limited by the small diffusion barrier of the monomer of less than 0.1 eV. Further, the formation routes for the 4H atom clusters are also presented. The current study can serve as a foundation to systematically model H atom clustering in metals and alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Post-processing interstitialcy diffusion from molecular dynamics simulations

An algorithm to rigorously trace the interstitialcy diffusion trajectory in crystals is developed. The algorithm incorporates unsupervised learning and graph optimization which obviate the need to input extra domain specific information depending on crystal or temperature of the simulation. The algorithm is implemented in a flexible framework as a post-processor to molecular dynamics (MD) simulations. We describe in detail the reduction of interstitialcy diffusion into known computational problems of unsupervised clustering and graph optimization. We also discuss the steps, computational efficiency and key components of the algorithm. Using the algorithm, thermal interstitialcy diffusion from low to near-melting point temperatures is studied. We encapsulate the algorithms in a modular framework with functionality to calculate diffusion coefficients, migration energies and other trajectory properties. The study validates the algorithm by establishing the conformity of output parameters with experimental values and provides detailed insights for the interstitialcy diffusion mechanism. The algorithm along with the help of supporting visualizations and analysis gives convincing details and a new approach to quantifying diffusion jumps, jump-lengths, time between jumps and to identify interstitials from lattice atoms. -- Graphical abstract:.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2011

In situ transmission electron microscopy of electron-beam induced damage process in nuclear grade graphite

Atomic level processes involved in the swelling and crack-closing in nuclear grade graphite under electron irradiation have been observed in real-time using transmission electron microscopy. Noise-filtered lattice images show the formation of vacancy loops, interstitial loops and resulting dislocations with unprecedented clarity. The dislocation dipoles formed via vacancy loops were found to undergo climb resulting in extra basal planes. Concurrent EELS studies showed a reduction in the atomic density because of the breakage of hexagonal carbon rings. The formation of new basal planes via dislocation climb in addition to the bending/breaking of basal planes leads to swelling and closing of micro-cracks.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Fast ionic conduction achieved through the design and synthesis of ceramic heterointerfaces

Lithium (Li) chloride and iron oxychloride (FeOCl), typically nonconductive, were combined to form a [Li 1+δ Cl] δ+ /[FeOCl] δ- heterointerface composite material (LFH), achieving ionic conductivities of >1 mS cm -1 . Analysis techniques (scanning transmission electron microscopy [STEM] and electron energy-loss spectroscopy [EELS]) indicated that the microstructure of LFH consisted of an amorphous LiCl-based shell surrounding a crystalline FeOCl-based core. Electrochemical measurements alongside solid-state 6,7 Li nuclear magnetic resonance (NMR) and molecular dynamic simulations revealed Li+ as the sole conductive species, with a diffusion barrier of ~0.25 eV. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) results further supported interstitial Li + diffusion at the heterointerface and within the LiCl phase, made possible by the heterointerface. Despite susceptibility to electronic conductivity, iron’s defects and multivalency (Fe³⁺, Fe²⁺) enable the Fe–O–Cl framework to accept Cl - , facilitating Li⁺ ionic conduction. Finally, a prototype solid-state cell (showing 97% Coulombic efficiency) demonstrated the viability of this heterointerface design for applications in energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Insertion-release of guest species and ionic conduction in polyoxometalate solids with a layer-like Anderson structure

The precipitation of Na{sup +} and K{sup +} mixed salts of Anderson type [SbW{sub 6}O{sub 24}]{sup 7-} by addition of excess of NaNO{sub 3} and NaCl yielded polycrystalline powders of Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2), respectively. The two compounds are isomorphous and exhibit a layer-like Anderson (LLA) type structure, which consists of [SbW{sub 6}O{sub 24}]{sup 7-}-containing layers and interstitial Na{sup +}, K{sup +}, NO{sub 3}{sup -} or Cl{sup -}, and water O atoms. Recrystallization of 1 and 2 from hot water yielded Na{sub 2}K{sub 5.4}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.4}.12H{sub 2}O (1-recry) and Na{sub 2}K{sub 5.25}[SbW{sub 6}O{sub 24}]Cl{sub 0.25}.12H{sub 2}O (2-recry) as a result of partial release of NO{sub 3}{sup -} and Cl{sup -} (and Na{sup +} and K{sup +} for charge compensation). Dehydration of 1 and 2 at 400 and 500 {sup o}C (1-dehyd400 and 2-dehyd500) caused a shrinkage of lattice, but their the LLA structures retained. Simulation of X-ray diffraction (XRD) patterns for the dehydrated forms allowed to presume that the each [SbW{sub 6}O{sub 24}]{sup 7-} anion had been 30{sup o}-rotated within its molecular plane in order to avoid intermolecular repulsion. A compressed powder of 1-dehyd400 exhibited fast alkaline-ion conduction with a bulk conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. The hosting of a sufficient amount of NO{sub 3}{sup -} together with Na{sup +} for charge compensation into the lattice is crucial for high conduction. -- Graphical abstract: Two compounds Na{sub 2.5}K{sub 5.3}[SbW{sub 6}O{sub 24}](NO{sub 3}){sub 0.8}.12H{sub 2}O (1) and Na{sub 2}K{sub 5.35}[SbW{sub 6}O{sub 24}]Cl{sub 0.35}.12H{sub 2}O (2) possessing a layer-like Anderson (LLA) structure exhibited pseudo intercalation-deintercalation behavior. The dehydrated form of 1 is a high alkaline cation conductor with a conductivity of 1.2x10{sup -2} {Omega}{sup -1} cm{sup -1} at 400 {sup o}C. Display Omitted Research highlights: {yields} Layer-like Anderson-type POM solid accommodates and releases NO{sub 3}{sup -} and Cl{sup -}. {yields} The POM exhibits reversible dehydration by heat treatment. {yields} The dehydration involves rotation of POM molecule retaining layer structure. {yields} The dehydrated POM shows good Na{sup +} and K{sup +} conduction.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Microstructure and magnetic properties of electrospun one-dimensional Al{sup 3+}-substituted SrFe{sub 12}O{sub 19} nanofibers

SrAl{sub x}Fe{sub 12-x}O{sub 19} (x=0-3.0) nanofibers with diameters about 100 nm have been prepared by electrospinning and subsequent heat treatment. With Al{sup 3+} ion content ranging from 0 to 3.0, the lattice parameters decrease due to Fe{sup 3+} ions substituted by smaller Al{sup 3+} ions and the average grain size calculated by the Scherrer's equation reduces from 65 to 37 nm. The magnetization shows a continuous reduction with the Al content and its value measured at 77 K is higher than at room temperature, which can be explained by Bloch's law. For the coercivity, its value initially increases, reaching a maximum value of 617 (298 K) and 547 kA m{sup -1} (77 K) at x=2.0, and then reduces with the Al content further increase largely arising from the substituted Al{sup 3+} ion arrangement in different interstitial sites of the strontium ferrite unit cell. -- Graphical abstract: Al{sup 3+} ions substituted strontium ferrite nanofibers have been prepared by the electrospinning with a diameter of about 100 nm and the Al{sup 3+} ion substitution has a great effect on the microstructure and magnetic property of SrAl{sub x}Fe{sub 12-x}O{sub 19} nanofibers. Display Omitted Research highlights: {yields} SrAl{sub x}Fe{sub 12-x}O{sub 19} nanofibers have been fabricated by the electrospinning. {yields} There is a relation between the Al{sup 3+} ions substitution and microstructure. {yields} The magnetic property can be tuned effectively by Al{sup 3+} ion substitution. {yields} The magnetic property is influenced by measurement temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Preparation, crystal structure, and superconductive characteristics of new oxynitrides (Nb{sub 1-x}M{sub x})(N{sub 1-y}O{sub y}) where M=Mg, Si, and x{approx}y

New niobium oxynitrides containing either magnesium or silicon were prepared at 1000 deg. C by ammonia nitridation of oxide precursors obtained via the citrate route. The products had rock-salt type crystal structures. Crystallinity was improved by annealing in 0.5 MPa N{sub 2} and the final compositions were (Nb{sub 0.95}Mg{sub 0.05})(N{sub 0.92}O{sub 0.08}) at 1500 deg. C and (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) at 1200 deg. C. The magnesium and oxide ions partially co-substitute the niobium and nitride ions in the octahedral sites of the {delta}-NbN lattice, respectively. Silicon ions were also successfully doped together with oxide ions into the rock-salt type NbN lattice. The Si doped product exhibited relatively large displacement at the octahedral sites and was accompanied by a small amount of cation vacancies. Superconductivity was improved by annealing to obtain critical temperatures/volume fractions of T{sub c}=17.6 K/100% for Mg- and T{sub c}=16.2 K/95% for the Si-doped niobium oxynitrides. - Graphical Abstract: Doped silicon ions substituting Nb in (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) introduced a large displacement at the 4a site mainly because of the accompanied vacancy. The silicon ions may also be slightly shifted from the regular octahedral 4a site (green) towards the interstitial tetrahedral site (red) statistically in the rock-salt type lattice. Highlights: > New superconducting niobium oxynitrides containing either magnesium or silicon were prepared. > Their annealed products had chemical compositions of (Nb{sub 0.95}Mg{sub 0.05})(N{sub 0.92}O{sub 0.08}) and (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) in the rock-salt type structure. > Their superconductivities were T{sub c}/volume fraction=17.6 K/100% and 16.2 K/95%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Thermal expansion in 3d-metal Prussian Blue Analogs-A survey study

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M{sup II}{sub 3}[(M'){sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O and M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O, where M{sup II}=Mn, Fe, Co, Ni, Cu and Zn, (M'){sup III}=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between -150 deg. C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3-bar m, F4-bar 3m and Pm3-bar m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7x{sup 1}0{sup -6} K{sup -1} for Co{sub 3}[Co(CN){sub 6}]{sub 2}.12H{sub 2}O. All of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O compounds show negative thermal expansion behavior, which correlates with the Irving-Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M{sup II}{sub 3}[Fe{sup III}(CN){sub 6}]{sub 2}.nH{sub 2}O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M{sup II}{sub 2}[Fe{sup II}(CN){sub 6}].nH{sub 2}O compounds show positive thermal expansion behavior. - Graphical Abstract: The structure of Prussian Blue analogs (PBAs) consists of two types of metal centered octahedral units connected by cyanide ligand. Lattice and interstitial water molecules are present in these framework structures. All the PBAs of the M{sub 3}[Co(CN){sub 6}]{sub 2}.nH{sub 2}O family show negative thermal expansion (NTE) behavior. The lattice parameters and magnitude of NTE correlates inversely with the Irving-Williams series of metal complex stability. Highlights: > Thermal expansion behavior of 17 Prussian Blue Analogs has been studied via XRD. > Nine compounds display negative thermal expansion (NTE) behavior. > All compounds of the M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} family exhibit NTE behavior. > Magnitude of the NTE in M{sup II}{sub 3}[Co{sup III}(CN){sub 6}]{sub 2} follows the order Mn>Fe>Co>Ni>Cu<Zn. > NTE materials show correlations with lattice parameters and Irving-Williams series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

(Na{sub x}k{sub 1−x}){sub 2}Ta{sub 4}O{sub 11}(x≈0.93) piezoelectric phase from the transformation of Ta{sub 2}O{sub 5} thin films of monoclinic structure

A phase of trigonal structure has been reported in previous articles to be piezoelectric with a very high longitudinal d{sub 33} coefficient of several thousand pm/V (J. Solid State Chem. 184 (2011) 2023, 2033). It was observed in Ta{sub 2}O{sub 5} thin films and assumed to be the result of a reversible monoclinic–trigonal phase transition. However, new investigations are reported because the cell parameters of this phase are actually very close to those of the natrotantite mineral Na{sub 2}Ta{sub 4}O{sub 11}. From analyses by X-ray energy dispersive spectroscopy (XEDS), the chemical composition of this trigonal phase corresponds to (Na{sub x}K{sub 1−x}){sub 2}Ta{sub 4}O{sub 11} with x≈0.93. The origin of sodium, potassium, iron and oxygen atoms is found to be due to a pollution coming from alumina crucibles used for thermal treatments. Knowing both atomic structures Ta{sub 2}O{sub 5} and Na{sub 2}Ta{sub 4}O{sub 11} and their structural relationships, observed by high resolution transmission electron microscopy (HRTEM), the mechanism of the reaction of transformation is re-examined and discussed. This mechanism implies that Ta{sup 5+} vacancies likely exist in monoclinic structures of tantalum oxide and that electrical neutrality could be due to incorporated proton H{sup +} instead of O{sup 2−} vacancies or Ta{sup 5+} interstitials. - Graphical abstract: (a, b) TEM images of interfaces between Ta{sub 2}O{sub 5} monoclinic and (Na{sub 0.93}K{sub 0.07}){sub 2}Ta{sub 4}O{sub 11} trigonal phases where it appears that the ratio of periods for the transformation monoclinic-to-trigonal is 3/2 (c, d) corresponding schema of the reaction of transformation, (a, c) viewed along the zone axes [010]{sub o}∥[1{sup ¯}21{sup ¯}]{sub R} and (b, d) along the zone axes [100]{sub o}∥[101{sup ¯}]{sub R}. Highlights: ► The formation of a piezoelectric phase in Ta{sub 2}O{sub 5} thin films, reported in previous articles, is re-examined. ► Its composition is actually (Na{sub x},K{sub 1}−x){sub 2}Ta{sub 4}O{sub 11} with x=0.93, instead of Ta{sub 2}O{sub 5}. ► Ta{sup 5+} vacancies, compensated by protons within tantalumoxide, are involved in a new analysis of the transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Defect disorder in UO{sub 2}

A defect disorder model has been developed to determine equilibrium off-stoichiometry and its spatial variations in UO{sub 2} crystals. The model gives the concentrations of atomic defects and electronic carriers as functions of oxygen partial pressure and temperature in the bulk and near crystal surfaces subject to an oxygen environment. Energetic parameters from published density functional theory calculations have been integrated into the defect disorder model for an accurate determination of the defect density and off-stoichiometry. The ionosorption theory has been used to couple the oxygen environment with the defect state in the crystal as we solved for the defect disorder near crystal surfaces. Contrary to the common belief that hyper-stoichiometry of UO{sub 2} is dominated by oxygen interstitials, the current model predicts that this regime is rather dominated by uranium vacancies. The model predictions also show that, in the presence of surfaces, the point defect concentrations vary by orders of magnitude in the subsurface region relative to the bulk region. Highlights: • Defect disorder in bulk UO2+x is modeled in terms of temperature and oxygen pressure. • The densities of atomic defects and electronic charge carriers are determined. • The model is extended to study the heterogeneity of defect density near crystal surfaces. • The surface effect is modeled using ionosorption theory. • The dominant defect type and off-stoichiometry profile near surface are found.

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

Effects of size reduction on microstructural, optical, vibrational, magnetic and photocatalytic properties of ZnO nanocrystals

Highlights: • ZnO nanocrystals of different sizes 4–19 nm, thus different S/V ratios synthesized. • Lattice strain and lattice volume increase with size reduction. • Raman spectra show enhanced surface effects with phonon mode disappearance. • ESR shows exchange interaction; VSM shows surface originated ferromagnetism. • Photocatalysis is less affected with size reduction and surface enhancement. - Abstract: ZnO nanocrystals were synthesized in the size range 4 nm–19 nm by chemical co-precipitation method and extensively characterized by various techniques. Size control was achieved by changing the concentration of ME that acted as the capping agent. Lattice strain and lattice volume were found to increase with the decrease in crystallite size that could be attributed to an enhanced influence of surface atoms. Raman spectroscopy provided evidence of enhancement of surface influence and reduction of crystallinity with the observation of decrease in E{sub 2}{sup high} phonon mode intensity with a decrease in crystallite size. Electron spin resonance spectra revealed the presence of exchange interaction as well as presence of lattice disorder. Vibrating sample magnetometry results showed that M-H curves exhibit hysteresis loops which confirmed the ferromagnetic nature of the nanocrystals and it could be attributed to the interaction between localized electron spins resulting from oxygen vacancies at the surface. Blue shift of the UV–Visible absorption spectra was observed with decrease in crystallite size, which could be attributed to quantum confinement effect. Room temperature photoluminescence spectra were recorded under UV light excitation, which showed emission of different colours (light violet, violet, blue and green) in the visible region, attributable to the presence of various types of defects such as zinc interstitial, zinc vacancy and oxygen vacancy in the ZnO nanocrystals. Photodegradation of aqueous methylene blue by the ZnO nanocrystals was performed under simulated sunlight irradiation. There was a very small increase in efficiency of photodegradation with size reduction, which showed that there was no significant change in surface defects with size reduction in the nanocrystals despite the surface enhancement. A mechanism for photocatalysis involving defect states has been proposed.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2011

Unusual ferromagnetism in high purity ZnO sintered ceramics

We report our novel result regarding the observation of unusual but clean ferromagnetic (FM) signature at room temperature (RT) in high pure (99.999%) ZnO bulk ceramics processed by slow step sintering schedule (SSSS). All the sintered samples showed ferromagnetic signature at room temperature. However, sample sintered at 850 {sup o}C showed more prominent M-H loop and saturation magnetization with respect to samples sintered at 500 {sup o}C and 1300 {sup o}C. Observation of FM behavior in sintered ceramics may be attributed to the presence of defects like cation (Zn)/anion (O) vacancies and interstitials created during the processing of sample. It is anticipated that SSSS promotes enhanced physical bulk as well as surface densification and at the same time confined the outgassing of free oxygen and Zn from the bulk which are acting as suitable defect sites inside the sintered grains and grain boundary junctions. Our micro-Raman and X-ray photoelectron studies revealed the existence of these defects which are believed to be the origin of the unconventional ferromagnetism (FM) of ZnO bulk ceramic at room temperature.

36 MATERIALS SCIENCE↗