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At least 631 records · Page 35

Determination of Thermal Expansion, Defect Formation Energy, and Defect-Induced Strain of α-U Via ab Initio Molecular Dynamics

Uranium (U) is often alloyed with molybdenum (Mo) or zirconium (Zr) in order to stabilize its high-temperature body-centered cubic phase for use in nuclear reactors. However, in all metallic fuel forms, the α phase of U remains in some fraction. This phase decomposition due to temperature or compositional variance can play an outsized role on fuel performance and microstructural evolution. Relatively little is known about fundamental point defect properties in α -U at non-zero temperatures, from either computational or experimental studies. This work performs the first thorough evaluation of the α phase of U via ab initio molecular dynamics (AIMD). A number of thermophysical properties are calculated as a function of temperature, including equilibrium lattice parameters, thermal expansion, and heat capacity. These results indicate a two-region behavior, with the transition at 400 K. The thermal expansion/contraction in the a / b direction occurs rapidly from 100 up to 400 K, after which a more linear and gradual change in the lattice constant takes place. The volumetric expansion matches experiments quantitatively, but the individual lattice constant expansion only matches experiments qualitatively. Point defect formation energies and induced lattice strains are also determined as a function of temperature, providing insight on defect populations and the fundamentals of irradiation growth in α -U. Interstitials induce significantly more strain than vacancies, and the nature of that strain is highly dependent on the individual lattice directions. The direction of point defect-induced lattice strain is contrary to the irradiation growth behavior of α -U. This work shows that isolated point defects cannot be the primary driving force responsible for the significant irradiation-induced growth of α -U observed experimentally.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Imaging coherent phonons and precursor dynamics in LaFeAsO with 4D ultrafast electron microscopy

In this work, we used 4D ultrafast electron microscopy (UEM) to directly image femtosecond photoinduced structural dynamics in single-crystal LaFeAsO at initial temperatures of 300 and 100 K, above and below the known structural and magnetic phase-transition temperatures, respectively. With nanometer-picosecond resolution, we resolved an initial (precursor) sigmoidlike response arising from photothermal expansion and lattice reorientation that precedes the onset of propagating coherent acoustic phonons (CAPs). In the specific regions probed, the precursor response at 100 K is shorter than at 300 K ($t$ 0.5;100 K = 11.3ps vs $t$ 0.5;300 K = 17.8ps), and the CAP oscillation frequency is lowered with cooling (ƒ CAP;100 K = 12 GHz vs ƒ CAP;300 K = 21 GHz), correlated to known lattice softening due to the structural phase change. The transient CAP behaviors at 300 K are dispersive, displaying an exponentially decaying phase velocity over the first nanosecond. Further, the CAP symmetry at 300 K matches a first-order antisymmetric shear mode (A 1 ), while at 100 K it is best matched by a mostly nondispersive zero-order symmetric mode (S 0 ). These findings illustrate the sensitivity of UEM imaging to spatially heterogeneous dynamics in the Fe-pnictide materials and more broadly in other quantum materials.

36 MATERIALS SCIENCE↗

Two-Dimensional Superconducting Fluctuations Associated with Charge-Density-Wave Stripes in La 1.87 ⁢Sr 0.13 ⁢Cu 0.99 ⁢Fe 0.01 ⁢O 4

The presence of a small concentration of in-plane Fe dopants in La 1.87 Sr 0.13 Cu 0.99 Fe 0.01 O 4 is known to enhance stripelike spin and charge density wave (SDW and CDW) order and suppress the superconducting T c . Here, we show that it also induces highly two-dimensional superconducting correlations that have been argued to be the signatures of a new form of superconducting order, the so-called pair density wave (PDW) order. In addition, using resonant soft x-ray scattering, we find that the two-dimensional superconducting fluctuation is strongly associated with the CDW stripe. In particular, the PDW signature first appears when the correlation length of the CDW stripe grows over eight times the lattice unit (~8 a). In conclusion, these results provide critical conditions for the formation of the PDW order.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Extreme sensitivity of the magnetic ground state to halide composition in FeCl 3 – x Br x

Mixed halide chemistry has recently been utilized to tune the intrinsic magnetic properties of transition-metal halides—one of the largest families of magnetic van der Waals materials. Prior studies have shown that the strength of exchange interactions, hence the critical temperature, can be tuned smoothly with halide composition for a given ground state. Here we show that the ground state itself can be altered by a small change of halide composition in FeCl 3–$x$ Br $x$ . Specifically, we find a threefold jump in the Néel temperature and a sign change in the Weiss temperature at $x$=0.08 corresponding to only 3% bromine doping. Using neutron scattering, we reveal a change of the ground state from spiral order in FeCl 3 to $A$-type antiferromagnetic order in FeBr 3 . From first-principles calculations, we show that a delicate balance between nearest and next-nearest neighbor interactions is responsible for such a transition. In conclusion, these results demonstrate how varying the halide composition can tune the competing interactions and change the ground state of a spiral spin liquid system.

2-dimensional systems↗

Waveform inversion of mantle Love waves: The born seismogram approach

Normal mode theory, extended to the slightly laterally heterogeneous Earth by the first-order Born approximation, is applied to the waveform inversion of mantle Love waves (200-500 sec) for the Earth's lateral heterogeneity at l=2 and a spherically symmetric anelasticity (Q sub mu) structure. The data are from the Global Digital Seismograph Network (GDSN). The l=2 pattern is very similar to the results of other studies that used either different methods, such as phase velocity measurements and multiplet location measurements, or a different data set, such as mantle Rayleigh waves from different instruments. The results are carefully analyzed for variance reduction and are most naturally explained by heterogeneity in the upper 420 km. Because of the poor resolution of the data set for the deep interior, however, a fairly large heterogeneity in the transition zones, of the order of up to 3.5% in shear wave velocity, is allowed. It is noteworthy that Love waves of this period range can not constrain the structure below 420 km and thus any model presented by similar studies below this depth are likely to be constrained by Rayleigh waves (spheroidal modes) only.

Tanimoto, T.↗

Waveform inversion of mantle Love waves - The Born seismogram approach

Normal mode theory, extended to the slightly laterally heterogeneous earth by the first-order Born approximation, is applied to the waveform inversion of mantle Love waves (200-500 sec) for the earth's lateral heterogeneity at l = 2 and a spherically symmetric anelasticity (Q sub mu) structure. The data are from the Global Digital Seismograph Network (GDSN). The l = 2 pattern is very similar to the results of other studies that used either different methods, such as phase velocity measurements and multiplet location measurements, or a different data set, such as mantle Rayleigh waves from different instruments. The results are carefully analyzed for variance reduction and are most naturally explained by heterogeneity in the upper 420 km. Because of the poor resolution of the data set for the deep interior, however, a fairly large heterogeneity in the transition zones, of the order of up to 3.5 percent in shear wave velocity, is allowed. It is noteworthy that Love waves of this period range can not constrain the structure below 420 km and thus any model presented by similar studies below this depth are likely to be constrained by Rayleigh waves (spheroidal modes) only.

Tanimoto, T.↗

Prediction of room-temperature multiferroicity in strained MoCr 2 S 6 monolayer

The contrasting d-orbital occupation required for ferroelectricity vs ferromagnetism makes it difficult for their coexistence in two-dimensional materials, especially at high temperature. To resolve this intrinsic contradiction, we propose a layered MoCr 2 S 6 multiferroics by alloying magnetic Cr element into the ferroelectric 1T phase of the MoS 2 matrix. First-principles calculations disclose that a spontaneous symmetry breaking, depending on the Mo atom displacement, leads to a robust ferroelectricity, which coexists with a ferromagnetic order originated from two neighboring Cr atoms. The effect can be further enhanced by tensile strain to bring about a room-temperature multiferroicity. Our results shed new light on the fundamental understanding of multiferroics and display promising applications in spintronics and multistate data storage.

2D materials↗

Phonon Spectroscopy in Antimony and Tellurium Oxides

α-Sb 2 O 3 (senarmontite), β-Sb 2 O 3 (valentinite), and α-TeO 2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here in this paper, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb 2 O 3 and β-Sb 2 O 3 , whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb–O–Sb wagging mode of α-Sb 2 O 3 whose frequency was not clear in most previous studies is experimentally observed for the first time at ~340 cm -1 . Softer lattice vibrational modes occur in orthorhombic β-Sb 2 O 3 compared to cubic α-Sb 2 O 3 , indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained β structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb 2 O 3 at 880 K accounts for about half of the α–β transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transparent metal model study of the use of a cellular growth front to form aligned monotectic composite materials

The purpose of this work was to resolve a scientific controversy in the understanding of how second phase particles become aligned during unidirectional growth of a monotectic alloy. A second aspect was to make the first systematic observations of the solidification behavior of a monotectic alloy during cellular growth in-situ. This research provides the first systematic transparent model study of cellular solidification. An interface stability diagram was developed for the planar to cellular transition of the succinonitrile glycerol (SNG) system. A method was developed utilizing Fourier Transform Infrared Spectroscopy which allows quantitative compositional analysis of directionally solidified SNG along the growth axis. To determine the influence of cellular growth front on alignment for directionally solidified monotectic alloys, the planar and cellular growth morphology was observed in-situ for SNG between 8 and 17 percent glycerol and for a range of over two orders of magnitude G/R.

Kaukler, William F.↗

High-Pressure Structural and Thermodynamic Properties of Cerium Orthosilicates (CeSiO 4 )

Pressure-induced phase transitions from the zircon structure-type (I4 1 /amd) to the scheelite structure type (I4 1 /a) are known for many ternary oxides systems (ABO 4 ). In this work, we present the first high-pressure study on synthetic stetindite (CeSiO 4 ) by a combination of in situ high-pressure synchrotron powder X-ray diffraction up to 36 GPa, implemented with and without dual sided laser heating, and in situ high-pressure Raman spectroscopy up to 43 GPa. Two phase transitions were identified: zircon to a high-pressure low-symmetry (HPLS) phase at 15 GPa and then to a scheelite at 18 GPa. The latter from HPLS scheelite phase was found irreversible; i.e., scheelite is fully quenchable at ambient conditions, as in other zircon-type phases. The bulk moduli (K 0 ) of stetindite, HPLS, and high-pressure scheelite phases were determined, respectively, as 171(5), 105(4), and 221(40) GPa by fitting to a second-order Birch-Murnaghan equation of state. The pressure derivatives of vibrational modes and Gru''neisen parameters of the zircon-structured polymorph are similar to those of other orthosilicate minerals. In conclusion, due to the larger ionic radii of Ce 4+ , with respect to Zr 4+ , stetindite was found to possess a softer bulk modulus and undergo the phase transitions at a lower pressure than zircon (ZrSiO 4 ), such observations are consistent with what were found in coffinite (USiO 4 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilization of three-dimensional charge order through interplanar orbital hybridization in Pr x Y 1–x Ba 2 Cu 3 O 6+δ

The shape of 3d-orbitals often governs the electronic and magnetic properties of correlated transition metal oxides. In the superconducting cuprates, the planar confinement of the d x 2 –y 2 orbital dictates the two-dimensional nature of the unconventional superconductivity and a competing charge order. Achieving orbital-specific control of the electronic structure to allow coupling pathways across adjacent planes would enable direct assessment of the role of dimensionality in the intertwined orders. Using Cu L 3 and Pr M 5 resonant x-ray scattering and first-principles calculations, we report a highly correlated three-dimensional charge order in Pr-substituted YBa 2 Cu 3 O 7 , where the Pr f-electrons create a direct orbital bridge between CuO 2 planes. With this we demonstrate that interplanar orbital engineering can be used to surgically control electronic phases in correlated oxides and other layered materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Alcove formation in dissolving cliffs driven by density inversion instability

We demonstrate conditions that give rise to cave-like features commonly found in dissolving cliffsides with a minimal two-phase physical model. Alcoves that are wider at the top and tapered at the bottom, with sharp-edged ceilings and sloping floors, are shown to develop on vertical solid surfaces dissolving in aqueous solvents. As evident from descending plumes, sufficiently large indentations evolve into alcoves as a result of the faster dissolution of the ceiling due to a solutal Rayleigh–Bénard density inversion instability. In contrast, defects of size below the boundary layer thickness set by the critical Rayleigh number smooth out, leading to stable planar interfaces. Furthermore, the ceiling recession rate and the alcove opening area evolution are shown to be given to first-order by the critical Rayleigh number. By tracking passive tracers in the fluid phase, we show that the alcoves are shaped by the detachment of the boundary layer flow and the appearance of a pinned vortex at the leading edge of the indentations. The attached boundary layer past the developing alcove is then found to lead to rounding of the other sides and the gradual sloping of the floor.

58 GEOSCIENCES↗

Mechanisms of in-plane magnetic anisotropy in superconducting NbSe 2

Here we present a unifying picture of the magnetic in-plane anisotropies of two-dimensional superconductors based on transition metal dichalcogenides. The symmetry considerations are first applied to constrain the form of the conductivity tensor. We hence conclude that the twofold periodicity of transport distinct from the planar Hall-related contributions requires a tensor perturbation. At the same time, the sixfold periodic variation of the critical field results from the Rashba spin-orbit coupling on a hexagonal lattice. We have considered the effect of a weak tensor perturbation on the critical field, gap function, and magnetoconductivity. The latter is studied using the time-dependent Ginzburg-Landau phenomenology. The common origin of the π periodicity in transport and thermodynamics properties is identified. The scheme constructed here is applied to describe the existing theoretical scenarios from a unified point of view. This allows us to single out the differences and similarities between the suggested approaches.

36 MATERIALS SCIENCE↗

Infinitely rugged intra-cage potential energy landscape in metallic glasses caused by many-body interaction

The absence of translational symmetry in glassy materials poses a significant challenge in establishing effective structure-property relationships in real space. Consequently, the potential energy landscape (PEL) in phase space is widely utilized to comprehend the complex phenomena in glasses. The classical PEL features a two-scale profile comprising mega-basins and sub-basins, corresponding to α-relaxations (e.g. glass transition) and β-relaxations (e.g. local cage-breaking atomic rearrangements), respectively. Recent studies, however, reveal that sub-basins are not smooth and contain finer structures, the origins of which remain elusive. Here we probe the smoothness of sub-basin bottoms in glasses' PEL by introducing small intra-cage cyclic loading and then measuring the net changes in atomic-level stresses. Compared to glasses with pair interaction, glasses with many-body interaction exhibit orders-of-magnitude larger and loading-dependent stress changes even before the first cage-breaking event takes place, which reflect much more feature-rich sub-basins. We further demonstrate this stark contrast stems from the spatial distribution of individual atom's constraining force field. Specifically, at vanishing perturbations, many-body interactions disrupt the positive-definite synchrony in energy variations of the perturbed atom and the whole system, causing inherently less confined atomic responses and infinitely rugged sub-basins. The implications of these findings for the selective addition or removal of fine structures in the PEL and the subsequent tuning of glassy materials' responses to external stimuli are also explored.

36 MATERIALS SCIENCE↗

Analysis of images obtained by the Phobos 2 spacecraft

The reflection spectrum and density of the Martian satellite, Phobos, suggests that it may be a captured C-type asteroid and hence may contain relatively unaltered organic material from the early history of the solar system. Since there is evidence from isotopic anomalies that meteorites presumably derived from such asteroids contain preserved interstellar material, it is conceivable that evidence for interstellar matter might also be present on Phobos. The present research concerns interpretation of the chemical composition of Phobos' surface and analysis of images of Phobos taken by the FREGAT camera equipment aboard the Phobos 2 Spacecraft, including both disk-integrated and disk-resolved photometry. Because the surface of Phobos is a regolith, spectral information on the surface composition will be convolved with information on the surface texture. A primary goal was to untangle these effects. Unfortunately, the Phobos 1 Spacecraft lost contact with Earth during its transit to Mars, and Phobos 2 likewise lost contact after two months in orbit around Mars. Thus, the hovering phase of very close approach and the landing of instruments on the surface of Phobos did not take place, so no data on the elemental composition of the surface is available. However, 37 images were obtained of the satellite. The results include the first such observations at near infrared wavelengths, for which disk-integrated results show that the corresponding geometric albedo is quite small and very similar to the value in the blue. The resolved surface photometry was analyzed by developing new methods of radiative transfer in rough surface layers and a procedure referred to as statistical photoclinometry. The results provide root mean square surface slopes on scales from the order of 1 millimeter to 250 meters, albedo fluctuations, and corresponding correlation lengths.

Irvine, W. M.↗

High Entropy Oxide Relaxor Ferroelectrics

Relaxor ferroelectrics are important in technological applications due to strong electromechanical response, energy storage capacity, electrocaloric effect, and pyroelectric energy conversion properties. Current efforts to discover and design materials in this class generally rely on substitutional doping as slight changes to local compositional order can significantly affect the Curie temperature, morphotropic phase boundary, and electromechanical responses. In this work, we demonstrate that moving to the strong limit of compositional complexity in an ABO 3 perovskite allows stabilization of relaxor responses that do not rely on a single narrow phase transition region. Entropy-assisted synthesis approaches are utilized to synthesize single-crystal Ba(Ti 0.2 Sn 0.2 Zr 0.2 Hf 0.2 Nb 0.2 )O 3 [Ba(5B)O] films. The high levels of configurational disorder present in this system are found to influence dielectric relaxation, phase transitions, nanopolar domain formation, and Curie temperature. Temperature-dependent dielectric, Raman spectroscopy, and second-harmonic generation measurements reveal multiple phase transitions, a high Curie temperature of 570 K, and the relaxor ferroelectric nature of Ba(5B)O films. The first-principles theory calculations are used to predict possible combinations of cations to design relaxor ferroelectrics and quantify the relative feasibility of synthesizing these highly disordered single-phase perovskite systems. Further, the ability to stabilize single-phase perovskites with various cations on the B-sites offers possibilities for designing high-performance relaxor ferroelectric materials for piezoelectric, pyroelectric, and electrocaloric applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chlorine in dense interstellar clouds - The abundance of HCl in OMC-1

The first detection of a chlorine-bearing molecular species in the interstellar medium via emission from the J = 1-0 transition of HCl at 625.9 GHz toward OMC-1 is reported. The relative strengths, widths, and velocities of the resolved hyperfine components are consistent with moderate optical depth emission originating from dense, quiescent molecular cloud material. The overall emission strength implies a fractional abundance of f(HCl/H2) of about (0.5-5.0) x 10 to the -8th, depending on the density of the emitting region. This is approximately an order of magnitude below previous theoretical estimates and a factor of 3-30 below the cosmic abundance of Cl. Recent laboratory work suggests that the lowered fractional abundance of HCl is caused by a combination of depletion onto grains with gas-phase loss processes such as the reaction of HCl with C(+).

Blake, G. A.↗

Low velocity opposed-flow frame spread in a transport-controlled environment DARTFire

The overall objectives of the DARTFire project are to uncover the underlying physics and increase understanding of the mechanisms that cause flames to propagate over solid fuels against a low velocity of oxidizer flow in a low-gravity environment. Specific objectives are (1) to analyze experimentally observed flame shapes, measured gas-phase field variables, spread rates, radiative characteristics, and solid-phase regression rates for comparison with previously developed model prediction capability that will be continually extended, and (2) to investigate the transition from ignition to either flame propagation or extinction in order to determine the characteristics of those environments that lead to flame evolution. To meet the objectives, a series of sounding rocket experiments has been designed to exercise several of the dimensional, controllable variables that affect the flame spread process over PMMA in microgravity, i.e., the opposing flow velocity (1-20 cm/s), the external radiant flux directed to the fuel surface (0-2 W/cm(exp 2)), and the oxygen concentration of the environment (35-70%). Because radiative heat transfer is critical to these microgravity flame spread experiments, radiant heating is imposed, and radiant heat loss will be measured. These are the first attempts at such an experimental control and measurement in microgravity. Other firsts associated with the experiment are (1) the control of the low velocity, opposed flow, which is of the same order as diffusive velocities and Stefan flows; (2) state-of-the-art quantitative flame imaging for species-specific emissions (both infrared and ultraviolet) in addition to novel intensified array imaging to obtain a color image of the very dim, low-gravity flames.

West, Jeff↗