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At least 631 records · Page 35

Synchroscan streak camera imaging at a 15-MeV photoinjector with emittance exchange

At the Fermilab A0 photoinjector facility, bunch-length measurements of the laser micropulse and the e-beam micropulse have been done in the past with a fast single-sweep module of the Hamamatsu C5680 streak camera with an intrinsic shot-to-shot trigger jitter of 10 to 20 ps. We have upgraded the camera system with the synchroscan module tuned to 81.25 MHz to provide synchronous summing capability with less than 1.5-ps FWHM trigger jitter and a phase-locked delay box to provide phase stability of {approx}1 ps over 10s of minutes. These steps allowed us to measure both the UV laser pulse train at 263 nm and the e-beam via optical transition radiation (OTR). Due to the low electron beam energies and OTR signals, we typically summed over 50 micropulses with 0.25-1 nC per micropulse. The phase-locked delay box allowed us to assess chromatic temporal effects and instigated another upgrade to an all-mirror input optics barrel. In addition, we added a slow sweep horizontal deflection plug-in unit to provide dual-sweep capability for the streak camera. We report on a series of measurements made during the commissioning of these upgrades including bunch-length and phase effects using the emittance exchange beamline and simultaneous imaging of a UV drive laser component, OTR, and the 800-nm diagnostics laser.

43 PARTICLE ACCELERATORS↗

Thermodynamics of gallium-stabilized delta-plutonium: A high-temperature drop calorimetry study

Throughout the Cold War (1947–1991), both the United States and the former Soviet Union independently derived a phase diagram for the Pu-Ga system that has different implications on Pu phase stability. In the phase diagram produced by the United States, the Pu δ-phase is thermodynamically stable at room temperatures when Ga content is between 2 and 9 at. %. The diagram produced by the Soviet Union shows the δ-phase undergoing an eutectoid decomposition into the α-Pu + α-Pu 3 Ga at 7.9 at. % Ga and 370 K. This would suggest that Ga-stabilized δ-Pu is metastable with respect to α-Pu + α-Pu 3 Ga at 298 K. To investigate this, and the thermodynamic behavior of Ga in the FCC lattice of δ-Pu, we have utilized high-temperature drop calorimetry to study the enthalpy of formation of two δ-Pu 1−x Ga x compositions. In doing so, mixing models (regular and subregular) were developed to understand the thermodynamic behavior of Ga in the FCC lattice of δ-Pu and found a strong departure from ideal conditions, which suggests Ga ordering in the FCC lattice of δ-Pu. Overall, it was found that δ-Pu 1−x Ga x is enthalpically metastable with respect to α-Pu + Pu 3 Ga at 298 K.

36 MATERIALS SCIENCE↗

Growth of different phases of yttrium manganese oxide thin films by pulsed laser deposition

Various phases of yttrium manganese oxide (YMO) thin films have been synthesized on different substrates from a single target of h-YMnO{sub 3}. It is observed that the phase stability and crystallinity of YMO thin films depend on the substrate used and oxygen partial pressure (OPP). (110) oriented and polycrystalline growth of h-YMnO{sub 3} are observed on the Al{sub 2}O{sub 3} (0001) and NGO (110) substrates respectively, when grown in OPP {approx_equal} 10{sup -6} Torr. While for similar OPP value, growth of mixed phases (h-YMnO{sub 3} and o-YMn{sub 2}O{sub 5}) is observed on Si (001) substrate. Oriented growth of O-YMn{sub 2}O{sub 5} phase film on Si (001) substrate is observed first time, when deposited at OPP value of 225 and 350 mTorr. +3 and mixed oxidation states (+3 and +4) of Mn were confirmed by x-ray photoelectron spectroscopy in pure YMnO{sub 3} phase and YMn{sub 2}O{sub 5} phase respectively.

36 MATERIALS SCIENCE↗

Theoretical investigations on the structure and properties of p-n-alkoxy benzoic acid based liquid crystals

The present study focused on the structural conformations, alkoxy chain lengths and mesogenic properties of two mole of alkoxy benzoic acid(nOBA) and one mole of suberic acid (SA) hydrogen bonded (nOBASA) complexes (n=8 to 10) by density functional theory (DFT) calculations and the Fourier Transform Infrared (FT-IR) spectrum. The intermolecular hydrogen bond formation was confirmed by the optimized geometric bond lengths and bond angles obtained by computation. Using the natural bond orbital (NBO) analysis, the stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed. Results obtained shows that the charge in electron density (ED) in σ*and π* antibonding orbital and second order delocalization energies E(2) authorizes the occurrence of intermolecular charge transfer. The molecular electrostatic potential (MEP) surface map is plotted over the optimized geometry of the molecule to obtain the chemical reactivity of the molecule. From the local charge distributions, the mesomorphic behavior and the nematic phase stabilities for each of the molecule have been predicted. Finally the calculated result is applied to simulated infrared spectra of 8OBASA mesogens which shows good agreement with the observed spectra. The comparison of the theoretical results obtained with the experimental ones shows the reliability of this DFT method.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Novel Superionic Na Conductors for Solid‐State Na batteries: Materials and Interface

This project aims to advance the fundamental understanding on how the cation or anion doping influence on the crystal structure, phase stability and ion transport of novel Na superionic conductors. Specifically, we focus on the Na 3-x A x SbS 4-y X y family solid electrolytes (A: cation dopant, X: anion dopant), a class of promising materials for all-solid-state sodium batteries owing to their high ionic conductivity and compositional tunability. By integrating materials synthesis, neutron scattering, and electrochemical characterization and theoretical simulations, this project sees to elucidate 1) how does the synthesis approaches (solid-state reaction, low-temperature reaction) on the phase purity and doping process; 2) how chemical doping (A: cation dopants such as Sn; X: anion dopants such as Se, F) modulate lattice dynamics and Na+ migration as well as interface stability toward Na metal. Specifically, this project’s proposed technology involves three objectives: (1) synthesize novel Na-ion conductors (anion or cation doped Na 3 SbS 4 ) with high phase purity and examine their structural features (e.g., phase stability); (2) understand Na-ion conductive properties of new Na-ion conductors through a combination of experimental characterizations and theoretical simulations; (3) investigate the interface stability of novel Na superionic conductors with electrode materials in solid-state Na batteries. These objectives will be achieved through combined experimental synthesis/characterizations and computational approaches. The obtained knowledge will provide a comprehensive synthesis-structure-property correlation, enabling the rational design of novel solid-state conductors with excellent conductivity and stability.

25 ENERGY STORAGE↗

A New Approach to Processing Rutile from Ilmenite Ore Utilizing the Instability of Pseudobrookite

Rutile (TiO{sub 2}) is a vital industrial material used in pigments and in many other valuable chemicals. A new production process to synthesize rutile from natural ilmenite ore and therefore overcome the environmental problems associated with conventional rutile extraction processes was developed. Because the simple phase separation of ilmenite (FeTiO{sub 3}) into Fe{sub 2}O{sub 3} and TiO{sub 2} occurs due to air oxidation, extracting TiO{sub 2} by removing Fe{sub 2}O{sub 3} may be possible if pseudobrookite (Fe{sub 2}TiO{sub 5}), known as a stable compound in the Fe{sub 2}O{sub 3}-TiO{sub 2} system at higher temperatures, is of unstable phase in the lower-temperature range. In order to clarify the potential of this new approach, the phase stability of pseudobrookite in the lower-temperature range is discussed. The free energy of formation of pseudobrookite from the respective pure oxides was measured at temperatures ranging from 1073 K to 1473 K by the chemical equilibrium technique using Al{sub 2}O{sub 3} as the reference oxide. The observed free energy is given as a function of temperature: ∆G{sup 0} = 7715 − 7.7T (J/mol). The results indicate that pseudobrookite has an unstable phase below 929 K. This has important industrial implications as a new approach to producing synthetic rutile from ilmenite ore by oxidation at low temperatures and acid leaching.

36 MATERIALS SCIENCE↗

Phase diagram of ammonium nitrate

Ammonium Nitrate (AN) is a fertilizer, yet becomes an explosive upon a small addition of chemical impurities. The origin of enhanced chemical sensitivity in impure AN (or AN mixtures) is not well understood, posing significant safety issues in using AN even today. To remedy the situation, we have carried out an extensive study to investigate the phase stability of AN and its mixtures with hexane (ANFO–AN mixed with fuel oil) and Aluminum (Ammonal) at high pressures and temperatures, using diamond anvil cells (DAC) and micro-Raman spectroscopy. The results indicate that pure AN decomposes to N{sub 2}, N{sub 2}O, and H{sub 2}O at the onset of the melt, whereas the mixtures, ANFO and Ammonal, decompose at substantially lower temperatures. The present results also confirm the recently proposed phase IV-IV{sup ′} transition above 17 GPa and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400°C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly stable polarization independent Mach-Zehnder interferometer

We experimentally demonstrate optical Mach-Zehnder interferometer utilizing displaced Sagnac configuration to enhance its phase stability. The interferometer with footprint of 27×40 cm offers individually accessible paths and shows phase deviation less than 0.4° during a 250 s long measurement. The phase drift, evaluated by means of Allan deviation, stays below 3° or 7 nm for 1.5 h without any active stabilization. The polarization insensitive design is verified by measuring interference visibility as a function of input polarization. For both interferometer's output ports and all tested polarization states the visibility stays above 93%. The discrepancy in visibility for horizontal and vertical polarization about 3.5% is caused mainly by undesired polarization dependence of splitting ratio of the beam splitter used. The presented interferometer device is suitable for quantum-information and other sensitive applications where active stabilization is complicated and common-mode interferometer is not an option as both the interferometer arms have to be accessible individually.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Ultrafast electron diffraction with radio-frequency compressed electron pulses

We report on the complete characterization of time resolution in an ultrafast electron diffraction (UED) instrument based on radio-frequency electron pulse compression. The temporal impulse response function of the instrument was determined directly in pump-probe geometry by performing electron-laser pulse cross-correlation measurements using the ponderomotive interaction. With optimal settings, a stable impulse response of 334{+-}10 fs was measured at a bunch charge of 0.1 pC (6.24 Multiplication-Sign 10{sup 5} electrons/pulse); a dramatic improvement compared to performance without pulse compression. Phase stability currently limits the impulse response of the UED diffractometer to the range of 334-500 fs, for bunch charges ranging between 0.1 and 0.6 pC.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Microstructure and thermal oxidation behavior of yttria-stabilized hafnia nanostructured coatings deposited on alumina

Nanostructured yttria-stabilized hafnia (YSH) coatings were grown on α-Al2O3 substrates with variable coating thickness in a wide range of ~50 nm to 1 μm. Microstructure and thermal oxidation behavior of the grown YSH coatings were studied employing X-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM) and isothermal furnace oxidation testing. The effect of coating thickness on the crystal structure, surface/interface morphology and thermal oxidation was investigated. X-ray diffraction analyses revealed the formation of monoclinic phase for relatively thin coatings (b100 nm) indicating that the interfacial phenomena play a dominant role in phase stabilization. The evolution towards stabilized cubic phase with increasing coating thickness is observed. The SEM results indicate the dense, columnar structure of YSH coatings as a function of thickness. Thermal oxidation measurements indicate the enhanced hightemperature oxidation resistance of cubic YSH coatings.

36 MATERIALS SCIENCE↗

Synthesis and Structural Characterization of Sb-Doped TiFe{sub 2}Sn Heusler Compounds

Ternary Heusler compounds form a numerous class of intermetallics, which include two families with general compositions ABC and AB{sub 2}C, usually referred to as half- and full-Heusler compounds, respectively. Given their tunable electronic properties, made possible by adjusting the chemical composition, these materials are currently considered for the possible use in sustainable technologies such as solar energy and thermoelectric conversion. According to theoretical predictions, Sb substitution in the TiFe{sub 2}Sn full-Heusler compound is thought to yield band structure modifications that should enhance the thermoelectric power factor. In this work, we tested the phase stability and the structural and microstructural properties of such heavily doped compounds. We synthesized polycrystalline TiFe{sub 2}Sn{sub 1−x}Sb{sub x} samples, with x = 0, 0.1, 0.2 and 1.0 by arc melting, followed by an annealing treatment. The structural characterization, performed by x-ray powder diffraction and microscopy analyses, confirmed the formation of the pseudo-ternary Heusler structure (cF16, Fm-3m, prototype: MnCu{sub 2}Al) in all samples, with only few percent amounts of secondary phases and only slight deviations from nominal stoichiometry. With increasing Sb substitution, we found a steady decrease in the lattice parameter, confirming that the replacement takes place at the Sn site. Quite unusually, the as-cast samples exhibited a higher lattice contraction than the annealed ones. The fully substituted x = 1.0 compound, again adopting the MnCu{sub 2}Al structure, does not form as stoichiometric phase and turned out to be strongly Fe deficient. The physical behavior at room temperature indicated that annealing with increasing temperature is beneficial for electrical and thermoelectrical transport. Moreover, we measured a slight improvement in electrical and thermoelectrical properties in the x = 0.1 sample and a suppression in the x = 0.2 sample, as compared to the undoped x = 0 sample.

36 MATERIALS SCIENCE↗

Density-functional theory for plutonium

We review here developments in the theoretical description and understanding of plutonium in terms of a metal with itinerant (band) 5f electrons. Within this picture most facets of this remarkable and anomalous material are accurately described by first-principle, parameter-free, density-functional-theory (DFT) calculations. We show that the model explains plutonium’s phase stability, elasticity, lattice vibrations, electronic structure, alloy properties, and magnetism. Fluctuations are addressed by means of constrained DFT calculations and new light is shed on the anomalous properties of δ plutonium, including explaining its negative thermal expansion. Effects of alloying and point defects in plutonium are also addressed. It is further emphasized that strong electron correlations, originating from a large intra-atomic Coulomb repulsion (~4 eV) of the 5f electrons, that has often been assumed for plutonium in the literature, is inconsistent with the experimental phase diagram of plutonium.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Electric field detection of coherent synchrotron radiation in a storage ring generated using laser bunch slicing

The electric field of coherent synchrotron radiation (CSR) generated by laser bunch slicing in a storage ring has been detected by an electro-optic sampling method. The gate pulses for sampling are sent through a large-mode-area photonic-crystal fiber. The observed electric field profile of the CSR is in good agreement with the spectrum of the CSR observed using Fourier transform far-infrared spectrometry, indicating good phase stability in the CSR. The longitudinal density profiles of electrons modulated by laser pulses were evaluated from the electric field profile.

43 PARTICLE ACCELERATORS↗

Nanoscale Insight into Lead-Free BNT-BT-xKNN

Piezoresponse force microscopy (PFM) is used to afford insight into the nanoscale electromechanical behavior of lead-free piezoceramics. Materials based on Bi{sub 1/2}Na{sub 1/2}TiO{sub 3} exhibit high strains mediated by a field-induced phase transition. Using the band excitation technique the initial domain morphology, the poling behavior, the switching behavior, and the time-dependent phase stability in the pseudo-ternary system (1-x)(0.94Bi{sub 1/2}Na{sub 1/2}TiO{sub 3}-0.06BaTiO{sub 3})-xK{sub 0.5}Na{sub 0.5}NbO{sub 3} (0 {le} x {ge} 18 mol%) are revealed. In the base material (x = 0 mol%), macroscopic domains and ferroelectric switching can be induced from the initial relaxor state with sufficiently high electric field, yielding large macroscopic remanent strain and polarization. The addition of KNN increases the threshold field required to induce long range order and decreases the stability thereof. For x = 3 mol% the field-induced domains relax completely, which is also reflected in zero macroscopic remanence. Eventually, no long range order can be induced for x {ge} 3 mol%. This PFM study provides a novel perspective on the interplay between macroscopic and nanoscopic material properties in bulk lead-free piezoceramics.

36 MATERIALS SCIENCE↗

Periodic optical variability of radio-detected ultracool dwarfs

A fraction of very low mass stars and brown dwarfs are known to be radio active, in some cases producing periodic pulses. Extensive studies of two such objects have also revealed optical periodic variability, and the nature of this variability remains unclear. Here, we report on multi-epoch optical photometric monitoring of six radio-detected dwarfs, spanning the ∼M8-L3.5 spectral range, conducted to investigate the ubiquity of periodic optical variability in radio-detected ultracool dwarfs. This survey is the most sensitive ground-based study carried out to date in search of periodic optical variability from late-type dwarfs, where we obtained 250 hr of monitoring, delivering photometric precision as low as ∼0.15%. Five of the six targets exhibit clear periodicity, in all cases likely associated with the rotation period of the dwarf, with a marginal detection found for the sixth. Our data points to a likely association between radio and optical periodic variability in late-M/early-L dwarfs, although the underlying physical cause of this correlation remains unclear. In one case, we have multiple epochs of monitoring of the archetype of pulsing radio dwarfs, the M9 TVLM 513–46546, spanning a period of 5 yr, which is sufficiently stable in phase to allow us to establish a period of 1.95958 ± 0.00005 hr. This phase stability may be associated with a large-scale stable magnetic field, further strengthening the correlation between radio activity and periodic optical variability. Finally, we find a tentative spin-orbit alignment of one component of the very low mass binary, LP 349–25.

79 ASTRONOMY AND ASTROPHYSICS↗

Excess entropy and crystallization in Stillinger-Weber and Lennard-Jones fluids

Molecular dynamics simulations are used to contrast the supercooling and crystallization behaviour of monatomic liquids that exemplify the transition from simple to anomalous, tetrahedral liquids. As examples of simple fluids, we use the Lennard-Jones (LJ) liquid and a pair-dominated Stillinger-Weber liquid (SW{sub 16}). As examples of tetrahedral, water-like fluids, we use the Stillinger-Weber model with variable tetrahedrality parameterized for germanium (SW{sub 20}), silicon (SW{sub 21}), and water (SW{sub 23.15} or mW model). The thermodynamic response functions show clear qualitative differences between simple and water-like liquids. For simple liquids, the compressibility and the heat capacity remain small on isobaric cooling. The tetrahedral liquids in contrast show a very sharp rise in these two response functions as the lower limit of liquid-phase stability is reached. While the thermal expansivity decreases with temperature but never crosses zero in simple liquids, in all three tetrahedral liquids at the studied pressure, there is a temperature of maximum density below which thermal expansivity is negative. In contrast to the thermodynamic response functions, the excess entropy on isobaric cooling does not show qualitatively different features for simple and water-like liquids; however, the slope and curvature of the entropy-temperature plots reflect the heat capacity trends. Two trajectory-based computational estimation methods for the entropy and the heat capacity are compared for possible structural insights into supercooling, with the entropy obtained from thermodynamic integration. The two-phase thermodynamic estimator for the excess entropy proves to be fairly accurate in comparison to the excess entropy values obtained by thermodynamic integration, for all five Lennard-Jones and Stillinger-Weber liquids. The entropy estimator based on the multiparticle correlation expansion that accounts for both pair and triplet correlations, denoted by S{sub trip}, is also studied. S{sub trip} is a good entropy estimator for liquids where pair and triplet correlations are important such as Ge and Si, but loses accuracy for purely pair-dominated liquids, like LJ fluid, or near the crystallization temperature (T{sub thr}). Since local tetrahedral order is compatible with both liquid and crystalline states, the reorganisation of tetrahedral liquids is accompanied by a clear rise in the pair, triplet, and thermodynamic contributions to the heat capacity, resulting in the heat capacity anomaly. In contrast, the pair-dominated liquids show increasing dominance of triplet correlations on approaching crystallization but no sharp rise in either the pair or thermodynamic heat capacities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-pressure synthesis and relationship between A-site ordering and local structure of multicomponent perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3}, Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Y

ABSTRACT: The synthesis of multicomponent perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3} (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Y) have been investigated using a high-pressure and high-temperature (6 GPa, 1175 °C) technique. When Ln{sup 3+} is larger La{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, the A-site ordered perovskites, LnMn{sub 3}(Al{sub 0.25}Ti{sub 0.75}){sub 4}O{sub 12} in Im-3, have been successfully synthesized. The A-site partially disordered one, (Sm{sub 0.80}Mn{sub 0.20})(Sm{sub 0.07}Mn{sub 0.93}){sub 3}(Al{sub 0.25}Ti{sub 0.75}){sub 4}O{sub 12} is also obtained. In the case of smaller Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, we have obtained no single phase but two decomposed perovskite phases. When Ln{sup 3+} is much smaller Y{sup 3+}, it is crystallized as an A-site disorder one in Pnma. The Rietveld structural refinements of the A-site ordered and partially disordered perovskites indicate that the tilting of (Al/Ti)O{sub 6} octahedrons for the A-site ions ordering is correlated with the (Al/Ti)–O and Ln–O bond lengths to optimize the coordination of the A- and A′-sites. The phase stability of the A-site ordered perovskites is discussed from the viewpoint of this correlation. - Graphical abstract: Ln{sup 3+} (VIII) ionic radius dependence of BO{sub 6} octahedron tilt angle and A/B–O distance of Im-3 perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3} (Ln=La-Sm).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge-tagged N-heterocyclic carbenes (NHC): Direct transfer from ionic liquid solutions and long-lived nature in the gas phase

Negatively charge-tagged N-heterocyclic carbenes have been formed in solution via deprotonation of imidazolium ions bearing acid side groups and transferred to the gas phase via ESI(–)-MS. The structure of the putative and apparently stable gaseous carbenes formed in such conditions were then probed via reactions with carbon dioxide using a triple quadrupole mass spectrometer particularly optimized for ion/molecule reactions of ESI-generated ions. Complete conversion to imidazolium carboxylates was achieved, which seems to demonstrate the efficiency of the transfer, the gas-phase stability, and the long-lived nature of these unprecedented charge-tagged carbenes and their predominance in the ionic population. Comprehensive studies on the intrinsic reactivity of N-heterocyclic carbenes with silent charge tags are therefore possible. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗