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At least 955 records · Page 53

Oxidation state and coordination environment of Pb in U-bearing minerals

This study examines the oxidation and coordination of lead (Pb) in the uranium (U) minerals uraninite (UO 2 ), coffinite (USiO 4 ), and brannerite (UTi 2 O 6 ), and minerals that have U as a minor constituent, zircon (ZrSiO 4 ) and titanite (CaTiSiO 5 ). The characterization of Pb was conducted through a combination of micro-synchrotron X-ray fluorescence mapping (µSXRF) and micro-X-ray absorption spectroscopy (µXAS), collected at the Pb L II and L III edge on characterized grains (electron microscopy and X-ray diffraction) from a range of geological settings and ages. For all minerals considered in this study, Pb L II and L III X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data indicate that Pb exists as Pb 2+ . In the case of uraninite, DFT structure optimization calculations suggest that the substitution of Pb 2+ for U 4+ is facilitated by the stereochemically active electron lone pair indicative of Pb 2+ , which effectively takes the place of an oxygen vacancy (coupled substitution Pb 2+ + = U 4+ + O 2- ). In detail, however, the EXAFS and XANES data, supported by first principle calculations of the XANES associated with Pb 2+ replacing U 4+ in the crystal lattice of uraninite, indicate that Pb 2+ is present in a less distorted coordination than suggested by DFT, which may reflect a yet to be characterized link between interstitial oxygen defects and Pb 2+ incorporation, rather than a simple oxygen vacancy. For coffinite, the XANES data demonstrate that Pb exists mainly as Pb 2+ in the form of galena, indicating limited stability of the isomorphous substitution in coffinite. In contrast, Pb is homogeneously distributed in the metamict mineral brannerite, which displays a distinct XANES spectrum suggestive of Pb 2+ bonded to oxygens in a highly distorted coordination environment. Pb L II XANES indicate that radiogenic Pb exists predominantly as Pb 2+ within the crystal lattice of zircon and as distinct mineral PbO nano-scale inclusions or domains. Additionally, Pb L II XANES measurements also indicate that Pb 2+ exists within titanite although the coordination environment is unclear. Overall, these data suggest that the previous indications of the presence of Pb 4+ in radioactive minerals need to be reconsidered. The nature of radiogenic Pb 2+ incorporation in U-bearing minerals controls the mobilization of Pb in hydrothermal fluids and the utility of a mineral as a geochronometer. The Pb valence and coordination data presented in this study provide fundamental constraints imperative for our understanding of the controls governing the mobilization of radiogenic Pb during water-rock interaction and metamorphism.

58 GEOSCIENCES↗

Pore-scale simulation of gas flow in microscopic permeable media with complex geometries

Lattice Boltzmann method (LBM) is an efficient tool to perform direct numerical simulation of gas flow in micro-size pores. Despite great advances in LBM and its use in describing gas flow in micro-size channels in slip and transitional flow regimes, exploring formulations that are able to capture flow behavior in domains with complex boundary geometries remains a challenging task. As a result, the impact of complexities in pore structures on gas flow may not be fully explored using LBM. In this study, we propose to use the combined bounce-back and Maxwellian diffusive reflection scheme to capture the slip velocity with a new set of slip coefficients. Optimal values of slip coefficients are determined using a gradient based method, where the results from the linearized Boltzmann equation is used as the reference solution. The proposed formulation is further validated against predictions from molecular dynamics simulation in the presence of complex geometries by introducing obstacles of different shapes in straight channels. LBM with the proposed boundary treatment is then used to investigate gas flow in a synthetic microscopic permeable medium. Here, results indicate that gas exhibits different flow configurations as Knudsen number varies, and apparent gas permeability appears to have up to a second-order dependency on the reciprocal mean pressure in slip and transitional flow regimes.

03 NATURAL GAS↗

Eco-friendly and effective strategy to synthesize ZnO/Ag{sub 2}O heterostructures and its excellent photocatalytic property under visible light

Highlights: • ZnO/Ag{sub 2}O photocatalysts with heterostructures were synthesized via a facile mechanochemical method. • The synthetic process does not involve any organic solvents and the reaction matrix can be recycled easily. • The synthetic method is gram-scale, and we can easily and routinely scale up this process to produce grams of the heterostructure nanomaterials. • The as-prepared samples without post-calcination show a high degree of crystallinity. - Abstract: ZnO/Ag{sub 2}O photocatalysts with heterostructure were synthesized by a green and effective mechanochemical method. The preparation process was taken in solid state at room temperature with a short grinding time. The as-made products showed a high degree of crystallinity without post-calcination treatment. Such synthetic method does not involve any organic solvents and the reaction matrix can be recycled. The as-prepared ZnO/Ag{sub 2}O samples show excellent photocatalytic activity and photostability for degradation of different organic dyes under visible light. The content of Ag{sub 2}O plays an important role in the photocatalytic activity, which can be tuned by the precursor AgNO{sub 3}. The photodegradation rate constant (k) of the optimal ZnO/Ag{sub 2}O sample under visible light is nearly 0.1004 min{sup −1} for methylene blue (MB), 0.063 min{sup −1} for rhodamine B (RHB) and 0.07 min{sup −1} for methyl orange (MO), which are much better than the pure ZnO (0.0075 min{sup −1}). The enhancement of the visible light photocatalytic activity could be attributed to the heterojunction interfaces induced by the match of crystal lattice and energy band between the Ag{sub 2}O and ZnO. The Ag{sub 2}O generates the excited-state electrons under visible light irradiation. The excited electrons on Ag{sub 2}O could directly transfer to the conduction band (CB) of ZnO, making ZnO/Ag{sub 2}O present remarkable visible light photocatalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Li + Diffusion in Amorphous and Crystalline Al 2 O 3 for Battery Electrode Coatings

Al 2 O 3 is often applied protectively to lithium-ion battery anode and cathode materials to inhibit surface degradation, suppress dendrite formation, and relieve mechanical stresses. Given the very high intrinsic band gap and diffusion barrier of the material, the mechanism that allows Li diffusion through these coatings is not well understood, and widely varying laboratory results indicate that there may be dependencies on morphology and stoichiometry. Using nudged elastic band calculations and ab initio molecular dynamics, we perform a systematic investigation across Al 2 O 3 structures, both crystalline and amorphous, and at various concentrations of Li + to uncover the optimal parameters for maximally diffusive coatings. We find a correlation between the low proximity of Li + to Al 3+ and the low Li + migration barrier. Although barriers are the lowest in the highly diffusive one-dimensional channels of crystalline θ-Al 2 O 3 , the system is structurally delicate and subject to detrimental distortion as the Li + content is increased. The α-Al 2 O 3 lattice is, conversely, highly stable against distortion at all Li + concentrations but disadvantageous for Li + migration. In amorphous systems, unscreened Li + –Li + Coulomb repulsion and pre-emptive occupation of “trapping sites” combine to lower the energy barriers as a function of increasing concentration. One of our most important findings is that Al-deficient materials can sharply increase Li + movement, and we predict that an amorphous material with a combination of high Li + concentration and Al deficiency would enable highly Li + -conductive protective coatings for electrodes.

25 ENERGY STORAGE↗

Efficient Control of Atom Arrangement in Ternary Metal Chalcogenide Nanoparticles Using Precursor Oxidation State

Controlling both the concentration and the distribution of elements in a given material is often crucial to extracting and optimizing synergistic properties of the various constituents. An interesting class of such multielement materials is metal chalcogenide nanoparticles, which exhibit a wide range of composition-dependent optoelectronic properties including both bandgap-mediated processes and localized surface plasmon resonance properties, each of which is useful in applications ranging from energy conversion to sensing. Because metal chalcogenide nanoparticles can support several different metal elements in a variety of chalcogen lattices, this material class has particularly benefited from the ability to control both atom concentration and atom arrangement to tailor final particle properties. The primary method to access complex, multimetallic chalcogenide particles is via a postsynthetic cation exchange strategy. One-pot syntheses have been less explored to access these complex particles, although this route is desirable for economy and scalability. In this work, we compare the composition and morphology outcomes from cation exchange and one-pot preparation approaches using a Cu/Ag/Se system, which is already known to exhibit both binary and ternary metal chalcogenide phases. We show that at similar concentrations of the two metal cations, initial reaction conditions for the one-pot method yield multicomponent nanoparticles, whereas cation exchange yields homogeneous ternary metal chalcogenide structures. We then show that by tuning the precursor oxidation state for the one-pot method, this approach can be used to access homogeneous ternary metal chalcogenide particles that are similar in atom arrangement to the particles obtained using cation exchange. Taken together, our results demonstrate reliable synthetic methods that yield a variety of controlled compositions and composition morphologies in the Cu/Ag/Se system. Importantly, we demonstrate that this entire collection of architectures can all be accessed via a one-pot method simply by modifying metal precursor chemistry. The mechanistic insights gained and the resulting streamlined syntheses outlined indicate pathways to easily scaled, highly tailorable syntheses for rapid translation into downstream technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the Bose glass–superfluid transition using quantum quenches of disorder

The disordered Bose–Hubbard model—a paradigm for strongly correlated and disordered bosonic systems1—is central to our understanding of quantum phase transitions2. Despite extensive theoretical work on the disordered Bose–Hubbard model, little is known about the impact of temperature, the dynamical behaviour of quantum phases, and how equilibrium is affected during quantum phase transitions. These issues are critically important to applications such as quantum annealing3,4,5,6,7 and electronics based on quantum phase transitions8. Here, we use a quantum quench of disorder in an ultracold lattice gas to dynamically probe the superfluid–Bose glass quantum phase transition at non-zero temperature ( Fig. 1). By measuring excitations generated during the quench, we provide evidence for superfluid puddles in the Bose glass phase and produce a superfluid–Bose glass phase diagram consistent with completely constrained, finite temperature, and equilibrium quantum Monte Carlo simulations. The residual energy from the quench, which is an efficacy measure for optimization through quantum annealing, is unchanged for quench times spanning nearly a hundred tunnelling times.

Physics↗

A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb –London –Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Breaking Rayleigh’s Law with Spatially Correlated Disorder to Control Phonon Transport

Controlling thermal transport in insulators and semiconductors is crucial for many technological fields such as thermoelectrics and thermal insulation, for which a low thermal conductivity (κ) is desirable. A major obstacle for realizing low κ materials is Rayleigh’s law, which implies that acoustic phonons, which carry most of the heat, are insensitive to scattering by point defects at low energy. We demonstrate, with large scale simulations on tens of millions of atoms, that isotropic long-range spatial correlations in the defect distribution can dramatically reduce phonon lifetimes of important low-frequency heat-carrying modes, leading to a large reduction of κ—potentially an order of magnitude at room temperature. We propose a general and quantitative framework for controlling thermal transport in complex functional materials through structural spatial correlations, and we establish the optimal functional form of spatial correlations that minimize κ. Finally, we end by briefly discussing experimental realizations of various correlated structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transition Core Modeling for Extended Enrichment & Accident-Tolerant Fuels Using Polaris/PARCS

Commercial light water reactor (LWR) operators and fuel vendors are currently interested in increasing the low-enriched uranium (LEU) fuel enrichments from the current limit of 5.0 $^w/_o$ $^{235}U$ up to 10 $^ w/_o$ $^{235}U$ (referred to as "LEU+") in their current fleets; they are also interested in using accident-tolerant fuel (ATF) with both LEU and LEU+ fuel. This report aims to identify modeling challenges and accuracy concerns in transition core analysis using the SCALE Polaris lattice physics code and U.S. Nuclear Regulatory Commission core simulator PARCS. At the time this study was started, no publicly available LEU+ core designs existed for boiling water reactor (BWR) or pressurized water reactor (PWR) systems. Therefore, fuel lattices were shuffled within a multi-assembly model to mimic neutronically challenging lattice combinations seen in transition cores, such as a fresh LEU+ lattice next to depleted LEU lattices. In addition to multi-assembly models, whole-core BWR transition core calculations were performed for ATF and LEU+ fuel using an existing Hatch-1 Cycle 3 core model. A whole-core BWR model was chosen due to the more heterogeneous core designs compared to those for a PWR core. Since the original core is an old checkerboard core design and no core or fuel design optimization was performed for the modeled fuel types, these core calculations were intended only to provide: (1) Comparisons of core characteristics of interest, such as the pin power distributions and peaking factors, Doppler temperature coefficients (DTCs), and control blade worths (CBWs) under challenging core designs, (2) Identification of reactor physics challenges in modeling LEU+ and ATF cores, and (3) A stress test for the Polaris/PARCS two-step modeling approach, including characterization of the relative accuracy for predicting characteristics of interest such as pin power distributions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Dialing in Direct Air Capture of CO 2 by Crystal Engineering of Bis-iminoguanidines

Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO 2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis-iminoguanidine (BIG) carbonate salts. Here, their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO 2 , and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ electric field X-ray total scattering reveals composition-dependent electromechanical strain mechanisms in (1 − x )BiFe 2/8 Ti 3/8 Mg 3/8 O 3 – x PbTiO 3 ceramics

Ferroelectric materials find many applications in energy and aerospace industries. A major challenge for ferroelectric materials is maintaining their properties at elevated temperatures. The (1 − x )BiFe 2/8 Ti 3/8 Mg 3/8 O 3 – x PbTiO 3 (BFTM–xPT) ferroelectric solid solution is a promising candidate for high-temperature applications as it has a high piezoelectric response while also maintaining its ferroelectric phase until a high Curie temperature (T C ) of 650 °C. In this work, we investigate the piezoelectric mechanism in BFTM–xPT, a novel high-T C ferroelectric ceramic. To elucidate the origin of its enhanced piezoelectric performance, relative to other piezoceramics of similar T C , in situ electric field X-ray total scattering experiments were performed. Total scattering combines Bragg scattering (diffraction) and diffuse scattering (pair distribution function), providing insight on various length scales. With information spanning different length scales, extrinsic contributions (i.e., domain wall motion and interphase boundary motion) can be separated from intrinsic contributions (i.e., piezoelectric lattice strain). We show that, for compositions within the morphotropic phase boundary (MPB, x = 0.325), the piezoelectric response is dominated by intrinsic piezoelectric lattice strain, whereas outside the MPB (x = 0.375) the major component of the piezoelectric response is from extrinsic mechanisms including an electric-field-induced phase transition and tetragonal domain wall motion. This article reveals that the origin of piezoelectric response in BFTM–xPT is composition-dependent and shows that high-performance materials may also be located outside the MPB. These findings can help guide material design to optimize properties for specific applications.

Richtik, Brooke N. [University of Calgary, AB (Can↗

Fabrication of FCC-SiO{sub 2} colloidal crystals using the vertical convective self-assemble method

In order to determine the optimal conditions for the growth of high-quality 250 nm-SiO{sub 2} colloidal crystals by the vertical convective self-assemble method, the Design of Experiments (DoE) methodology is applied. The influence of the evaporation temperature, the volume fraction, and the pH of the colloidal suspension is studied by means of an analysis of variance (ANOVA) in a 3{sup 3} factorial design. Characteristics of the stacking lattice of the resulting colloidal crystals are determined by scanning electron microscopy and angle-resolved transmittance spectroscopy. Quantitative results from the statistical test show that the temperature is the most critical factor influencing the quality of the colloidal crystal, obtaining highly ordered structures with FCC stacking lattice at a growth temperature of 40°C.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Robust and ultrafast state preparation by ramping artificial gauge potentials

Abstract The implementation of static artificial magnetic fields in ultracold atomic systems has become a powerful tool, e.g. for simulating quantum-Hall physics with charge-neutral atoms. Taking an interacting bosonic flux ladder as a minimal model, we investigate protocols for adiabatic state preparation via magnetic flux ramps. Considering the fact that it is actually the artificial vector potential (in the form of Peierls phases) that can be experimentally engineered in optical lattices, rather than the magnetic field, we find that the time required for adiabatic state preparation dramatically depends on which pattern of Peierls phases is used. This can be understood intuitively by noting that different patterns of time-dependent Peierls phases that all give rise to the same magnetic field ramp, generally lead to different artificial electric fields during the ramp. As an intriguing result, we find that an optimal choice allows for preparing the ground state almost instantaneously in the non-interacting system, which can be related to the concept of counterdiabatic driving. Remarkably, we find extremely short preparation times also in the strongly-interacting regime. Our findings open new possibilities for robust state preparation in atomic quantum simulators.

Wang, Botao (ORCID:0000000282202452)↗

Carbon nanotube quantum dots on hexagonal boron nitride

We report the fabrication details and low-temperature characteristics of carbon nanotube (CNT) quantum dots on flakes of hexagonal boron nitride (hBN) as substrate. We demonstrate that CNTs can be grown on hBN by standard chemical vapor deposition and that standard scanning electron microscopy imaging and lithography can be employed to fabricate nanoelectronic structures when using optimized parameters. This proof of concept paves the way to more complex devices on hBN, with more predictable and reproducible characteristics and electronic stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

E-field controlled phase transformation in bismuth ferrite thin films, and effect of laser energy density

Heterostructures of BiFeO 3 /Pb(Mg 1/3 Nb 2/3 )O 3 -30%PbTiO 3 (BFO/PMN-30PT) were fabricated here by pulsed laser deposition. Electric fields (E) were applied on the PMN-30PT substrates along the in-plane and out-of-plane directions, and the induced strain of BFO was measured as a function of E by X-ray diffraction. Reciprocal space maps along the (110) zone axis evidenced that a monoclinic M A phase was induced in both PMN-PT and BFO, where the dominate domain structures could be switched between biaxial directions under application of in-plane E. Studies were done for films prepared under different laser energy densities (LED), in order to optimize the in-plane strain of BFO. A relatively low LED of 1 J/cm 2 produced a better BFO thin film with larger in-plane strain.

36 MATERIALS SCIENCE↗

Dysprosium-doped cadmium oxide as a gateway material for mid-infrared plasmonics

The interest in plasmonic technologies surrounds many emergent optoelectronic applications, such as plasmon lasers, transistors, sensors and information storage. Although plasmonic materials for ultraviolet–visible and near-infrared wavelengths have been found, the mid-infrared range remains a challenge to address: few known systems can achieve subwavelength optical confinement with low loss in this range. With a combination of experiments and ab initio modelling, here we demonstrate an extreme peak of electron mobility in Dy-doped CdO that is achieved through accurate ‘defect equilibrium engineering’. In so doing, we create a tunable plasmon host that satisfies the criteria for mid-infrared spectrum plasmonics, and overcomes the losses seen in conventional plasmonic materials. In particular, extrinsic doping pins the CdO Fermi level above the conduction band minimum and it increases the formation energy of native oxygen vacancies, thus reducing their populations by several orders of magnitude. The substitutional lattice strain induced by Dy doping is sufficiently small, allowing mobility values around 500 cm 2 V –1 s –1 for carrier densities above 10 20 cm –3 . As a result, our work shows that CdO:Dy is a model system for intrinsic and extrinsic manipulation of defects affecting electrical, optical and thermal properties, that oxide conductors are ideal candidates for plasmonic devices and that the defect engineering approach for property optimization is generally applicable to other conducting metal oxides.

36 MATERIALS SCIENCE↗

The site occupation and valence of Mn ions in the crystal lattice of Sr{sub 4}Al{sub 14}O{sub 25} and its deep red emission for high color-rendering white light-emitting diodes

Highlights: • Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were identified using XANES and EPR. • Red luminescence was attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. • The Mn{sup 3+} incorporated in the center of AlO{sub 4} tetrahedron was non-luminescent. • The bond-valence theory was used to analyze the effective valences of cations. • A white LED device with CRI up to Ra 93.23 was packaged by using the red phosphor. - Abstract: The synthesis and component of red phosphor, Sr{sub 4}Al{sub 14}O{sub 25}: Mn, were optimized for application in white light-emitting diodes. The microstructure and morphology were investigated by the X-ray diffraction and scanning electron microscopy. Different valences of Mn ions in Sr{sub 4}Al{sub 14}O{sub 25} were discriminated using the electron paramagnetic resonance and X-ray absorption near-edge structure spectroscopy techniques. The bond-valence theory was used to analyze the effective valences of Sr{sup 2+} and Al{sup 3+} in Sr{sub 4}Al{sub 14}O{sub 25}. As a result, the strong covalence of Al{sup 3+} in the AlO{sub 4} tetrahedron other than in the AlO{sub 6} octahedron is disclosed. The deep red emission is attributed to Mn{sup 4+} occupying the center of AlO{sub 6} octahedron. The mechanism of energy transfer is mainly through dipole–dipole interaction, revealed by the analyses of critical distance and concentration quench. A high color rendering white LED prototype with color-rendering index up to Ra 93.23 packaged by using the red phosphor demonstrates its applicability.

36 MATERIALS SCIENCE↗

Optimization of Heat Treatment Cycles and Characterization of Aluminum Alloy AA7010

Multistage retrogression and reaging (RRA) heat treatment has been carried out on aluminum alloy AA7010. Each of the heat treatment steps for this alloy has been optimized on the basis of preliminary hardness and electrical conductivity measurements. These values were found to be a function of precipitate morphology and distribution. Samples were solution-treated (ST) with three different temperatures and quenching media, further aged at fixed temperature (120 °C) with time ranging from 24 to 120 h. Retrogression and reaging is done at 180-240 °C (for time duration of 2-60 min) and 120 °C (for 24-90 h), respectively. ST at 480 °C followed by warm water quenching (70 °C), aging cycle for T6 and T73 condition: 120 °C/42 h and 170 °C/128 h were found to be optimum. The optimum RRA conditions were achieved at retrogression parameters of 200 °C for 60 min and 240 °C for 60 min along with aging parameters of 120 °C/30 h and 120 °C/36 h, respectively. TEM images showed the presence of uniformly distributed precipitates in the matrix in RRA conditions. Statistical distribution of precipitates showed higher frequency of precipitates for RRA with optimized conditions RA1 (120 °C for 42 h + 200 °C for 60 min + 120 °C for 30 h) and RA2 (120 °C for 42 h + 240 °C for 60 min + 120 °C for 36 h).

36 MATERIALS SCIENCE↗