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At least 1,585 records · Page 88

High‐Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All‐Solid‐State Batteries

Abstract Superionic solid electrolytes (SEs) are essential for bulk‐type solid‐state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge‐transport properties, however a thorough understanding of how configurational entropy (ΔS conf ) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen‐rich lithium argyrodites with the general formula Li 5.5 PS 4.5 Cl x Br 1.5‐x (0≤x≤1.5). Using neutron powder diffraction and 31 P magic‐angle spinning nuclear magnetic resonance spectroscopy, the S 2− /Cl − /Br − occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li‐ion dynamics, leading to a room‐temperature ionic conductivity of 22.7 mS cm −1 (9.6 mS cm −1 in cold‐pressed state) for Li 5.5 PS 4.5 Cl 0.8 Br 0.7 (ΔS conf =1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li 5.5 PS 4.5 Cl 0.8 Br 0.7 SE allowed for stable cycling of single‐crystal LiNi 0.9 Co 0.06 Mn 0.04 O 2 (s‐NCM90) composite cathodes in SSB cells, emphasizing that dual‐substituted lithium argyrodites hold great promise in enabling high‐performance electrochemical energy storage.

Chemistry↗

The Role of Alkalis in Orchestrating Uranyl-Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, in this work, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb + and Cs + salts (Cs-U 1 and Rb-U 1 ). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li + , Na + and K + analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U 1 , the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO 2 in the solid-state, converting to Cs 4 [U VI O 2 (CO 3 ) 3 ], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U 1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsU V O 3 , where the parent phase has been computationally predicted, but not yet synthesized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DNP-enhanced ultrawideline solid-state NMR spectroscopy: Studies of platinum in metal–organic frameworks

Ultrawideline dynamic nuclear polarization (DNP)-enhanced 195 Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal–organic frameworks (MOFs). The 195 Pt SSNMR spectra, with breadths reaching 10,000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis - and trans -coordinated atomic Pt 2+ species supported on the UiO-66-NH 2 MOF. Here, the data revealed a dominance of kinetic effects in the formation of Pt 2+ complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt 2+ complex was confirmed in MOF-253.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Processing-Dependent Structure and Poroelasticity of Nafion in Liquid Water

Ionomers act as the solid polymer electrolyte membrane in many modern electrochemical devices, yet the role of their nanostructure in modulating the poroelastic response remains poorly understood, especially in liquid water, where few techniques can measure simultaneous transport-mechanical properties. Poroelastic Relaxation Indentation (PRI) is uniquely suited for measuring time-dependent transport-mechanical properties of porous solids, specifically hydraulic diffusivity, elastic modulus, Poisson’s ratio, and intrinsic permeability, for porous solids. While ionomers such as Nafion are not porous in the typical sense, Nafion has a nanophase-segregated structure that, when fully swollen in liquid water, behaves as a poroelastic solid with a coupled mechanical-transport response. Using a poroelastic framework, we investigate how casting and pretreatment of Nafion membranes alter their poroelastic response in liquid environments. We characterize both extruded and dispersion-cast Nafion membranes pretreated in water at 25 or 100 °C and relate the mechanical-transport properties to the ionomer structure via hydrophilic and intercrystalline domain spacing measured using Small-Angle X-ray Scattering (SAXS). At 25 °C, dispersion-cast membranes exhibit distinctly lower hydraulic diffusivity and intrinsic permeability than extruded membranes but with comparable mechanical properties. Pretreatment at 100 °C increases hydrophilic domain spacing, improving transport but at the expense of mechanical stiffness. Dispersion-cast membranes respond more strongly to pretreatment than extruded membranes. Using the Carman-Kozeny pore network model and the hydrophilic domain-spacing, we estimate the pore radius and tortuosity to show how pretreatment reduces structure-related tortuosity differences between dispersion-cast and extruded membranes. Here, in this work, we show that nanophase-segregated materials such as Nafion can be rigorously characterized using poroelasticity, resulting in physically meaningful transport-mechanical properties. Coupling PRI with SAXS provides insights into the nanostructural features that govern the coupled mechanical-transport response. By establishing PRI for a nanophase-segregated material, this approach opens avenues for this technique’s application in other hydrated polymeric materials not typically considered to be poroelastic.

Shen, Margaret [University of California, Berkeley↗

Study of SIDIS Unpolarized Cross Sections from a 3 He Target with the Solenoidal Large Intensity Device at JLab

In this paper we present a detailed impact study of semi-inclusive deep inelastic scattering unpolarized cross sections' measurements using the proposed SoLID apparatus at Jefferson Lab. This type of data, collected at large Bjorken $x_{bj}$, moderate values of $Q^2$ and small values of the transverse momentum of produced hadrons, $P_{hT}$, allows to study transverse momentum dependent (TMD) parton distribution and fragmentation functions in a still poorly explored region. We present the projected results for charged light mesons based on simulated data. For the azimuthal-angle integrated cross sections we adopt the TMD framework up to the next-to-next-to-next-to-leading-logarithmic (N3LL) accuracy, while a simpler TMD parton model is employed for the study of azimuthal angular dependencies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

In situ study of rotating lattice single–crystal formation in Sb 2 S 3 glass by Laue μXRD

Single–crystal architectures in glass, formed by a solid–solid transformation via laser heating, are novel solids with a rotating lattice. To understand the process of lattice formation that proceeds via crystal growth, we have observed in situ Sb 2 S 3 crystal formation under X–ray irradiation with simultaneous Laue micro X–ray diffraction (μXRD) pattern collection. By translating the sample with respect to the beam, we form rotating lattice single (RLS) crystal lines with a consistently linear relationship between the rotation angle and distance from nucleation site. The lines begin with a seed crystal, followed by a transition region comprising of sub–grain or very similarly oriented grains, followed by the presence of a rotating lattice single crystal of unrestricted length. Here, the results demonstrate that the primary cause of lattice rotation within RLS crystals is the densification accompanying the glass → crystal transformation, rather than stresses produced from the difference in thermal expansion coefficient of the two phases or paraelectric → ferroelectric transition during cooling to ambient temperature.

36 MATERIALS SCIENCE↗

Body-Centered Cubic Iron-Nickel Alloy in Earth's Core

Cosmochemical, geochemical, and geophysical studies provide evidence that Earth's core contains iron with substantial (5 to 15%) amounts of nickel. The iron-nickel alloy Fe 0.9 Ni 0.1 has been studied in situ by means of angle-dispersive x-ray diffraction in internally heated diamond anvil cells (DACs), and its resistance has been measured as a function of pressure and temperature. At pressures above 225 gigapascals and temperatures over 3400 kelvin, Fe 0.9 Ni 0.1 adopts a body-centered cubic structure. Our experimental and theoretical results not only support the interpretation of shockwave data on pure iron as showing a solid-solid phase transition above about 200 gigapascals, but also suggest that iron alloys with geochemically reasonable compositions (that is, with substantial nickel, sulfur, or silicon content) adopt the bcc structure in Earth's inner core.

36 MATERIALS SCIENCE↗

A comparison of measured and calculated upwelling radiance over water as a function of sensor altitude

A comparison is made between remote sensing data measured over water at altitudes ranging from 30 m to 15.2 km and data calculated for corresponding altitudes using surface measurements and an atmospheric radiative transfer model. Data were acquired on June 22, 1978 in Lake Erie, a cloudless, calm, near haze free day. Suspended solids and chlorophyll concentrations were 0.59 + or - 0.02 mg/1 and 2.42 + or - 0.03 micrograms/1 respectively throughout the duration of the experiment. Remote sensor data were acquired by two multispectral scanners each having 10 bands between 410 nm and 1040 nm. Calculated and measured nadir radiances for altitudes of 152 m and 12.5 km agree to within 16% and 14% respectively. The variation in measured radiance with look angle was poorly simulated by the model. It was concluded that an accurate assessment of the source of error will require the inclusion in the analysis of the contributions made by the sea state and specular sky reflectance.

Coney, T. A.↗

A theory for lateral wing-tip blowing

The concept of lateral blowing consists in utilizing thin jets of air, which are ejected in the spanwise direction from slots at the tips of straight and swept wings, or along the leading edges of delta wings, to generate aerodynamic forces without the assistance of deflecting solid surfaces. For weak intensities of blowing the so-generated forces could be used for roll and lateral control of aircraft. In this work a theory for this concept as applied to straight wings is presented, revealing the analytical relationship between blowing and aerodynamic forces. The approach is based on perturbing the span of an elliptically loaded wing. Scaling laws involving blowing intensity, aspect ratio, and angle of attack are derived and compared with experiments. It is concluded that this concept has potential as a novel roll and lateral control device.

Tavella, D.↗

Plasma produced by impacts of fast dust particles on a thin film

The thin-film impact plasma detector was pioneered by Berg for detecting small cosmic dust particles and measuring their approximate velocities in a time-of-flight configuration. While Berg's device was highly successful in establishing the flux of interplanetary dust, the accuracy of measuring the velocities of individual particles was a moderate 18 percent in magnitude and 27 degrees in angle. A much greater accuracy of less than or equal to 1 percent in determining the velocity components appears desirable in order to associate a particle with its parent body. In order to meet that need, research was initiated to determine if a thin-film detector can be designed to provide such accurate velocity measurements. Previous laboratory investigations of the impact plasma uncovered two difficulties: (1) solid or liquid spray is ejected from a primary impact crater and strikes neighboring walls where it produces secondary impact craters and plasma clouds; as a result, both quantity and time of detection of the plasma can vary significantly with the experiment configuration. Particles from an accelerator rarely have speeds v greater than or equal to 10-15 km/s, while cosmic dust particles typically impact at v = 10-72 km/s. The purpose of the tests discussed in this paper was to resolve the two difficulties mentioned. That is, the experiment configuration was designed to reduce the contribution of plasma from secondary impacts. In addition, most particles with v less than or equal to 25 km/s and all particles with v less than or equal to 10 km/s were eliminated from the beam.

Auer, Siegfried↗

Automated Laser Cutting In Three Dimensions

Computer-controlled machine-tool system uses laser beam assisted by directed flow of air to cut refractory materials into complex three-dimensional shapes. Velocity, position, and angle of cut varied. In original application, materials in question were thermally insulating thick blankets and tiles used on space shuttle. System shapes tile to concave or convex contours and cuts beveled edges on blanket, without cutting through outer layer of quartz fabric part of blanket. For safety, system entirely enclosed to prevent escape of laser energy. No dust generated during cutting operation - all material vaporized; larger solid chips dislodged from workpiece easily removed later.

Bird, Lisa T.↗

Investigating the origin of the far-field reflection interference fringe (RIF) of microdroplets

We show that the reflection interference fringe (RIF) is formed on a screen far away from the microdroplets placed on a prism-based substrate, which have low contact angles and thin droplet heights, caused by the dual convex–concave profile of the droplet, not a pure convex profile. The geometric formulation shows that the interference fringes are caused by the optical path difference when the reflected rays from the upper convex profile at the droplet–air interface interfere with reflection from the lower concave profile at oblique angles lower than the critical angle. Analytic solutions are obtained for the droplet height and the contact angle out of the fringe number and the fringe radius in RIF from the geometric formulation. Furthermore, the ray tracing simulation is conducted using the custom-designed code. The geometric formulation and the ray tracing show excellent agreement with the experimental observation in the relation between the droplet height and the fringe number and the relation between the contact angle and the fringe radius. This study is remarkable as the droplet's dual profile cannot be easily observed with the existing techniques. However, the RIF technique can effectively verify the existence of a dual profile of the microdroplets in a simple setup. In this work, the RIF technique is successfully developed as a new optical diagnostic technique to determine the microdroplet features, such as the dual profile, the height, the contact angle, the inflection point, and the precursor film thickness, by simply measuring the RIF patterns on the far-field screen.

42 ENGINEERING↗

Molecular ring rotation in solid ferrocene revisited

We report on quasielastic neutron spectroscopy experiments on ferrocene (bis(η{sup 5}-cyclopentadienyl)iron) in its three different crystalline phases: the disordered monoclinic crystalline phase (T > 164 K), the metastable triclinic phase (T < 164 K), and the stable orthorhombic phase (T < 250 K). The cyclopentadienyl rings in ferrocene are known to undergo rotational reorientations for which the analysis of our large data set suggests partially a revision of the known picture of the dynamics and allows for an extension and completion of previous studies. In the monoclinic phase, guided by structural information, we propose a model for rotational jumps among non-equivalent sites in contrast to the established 5-fold jump rotation model. The new model takes the dynamical disorder into account and allows the cyclopentadienyl rings to reside in two different configurations which are found to be twisted by an angle of approximately 30°. In the triclinic phase, our analysis demands the use of a 2-ring model accounting for crystallographically independent sites with different barriers to rotation. For the orthorhombic phase of ferrocene, we confirm a significantly increased barrier of rotation using neutron backscattering spectroscopy. Our data analysis includes multiple scattering corrections and presents a novel approach of simultaneous analysis of different neutron scattering data by combining elastic and inelastic fixed window temperature scans with energy spectra, providing a very robust and reliable mean of extracting the individual activation energies of overlapping processes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

X‐ray characterization of three possible edible oleogelators: Experiment and theory

Abstract Three oleogelator molecules (Triacontane (TC), Stearic acid (SA), and Behenyl Lignocerate (BL)) were studied individually, in pairs, or all together to make an oleogel using triolein as the oil. WAXS, SAXS and USAXS were used to elucidate the solid structures from angstroms to a few micrometers. A two‐dimensional mapping of atomic positions for each molecule was carried out to understand the crystalline multilayer structures formed. We assumed that the molecules were rigidly extended and that they underwent no significant (hindered) rotations so that the free energy is determined by the Lennard‐Jones interactions of closely packed multilayers. TC molecules were predicted to form a tilt angle of , yielding a SAXS line at Å ─1 , in acceptable agreement with the measured . For SA crystals (predicted) yielding a SAXS line at compared to (observed). No mixed crystals were observed for any pair of molecules or when all three were used. USAXS data showed that SA forms large nanocrystals compared to TC and BL. All three combinations of molecular pairs showed basic scatterers smaller or similar to those of individual molecules. The theory presented here, together with the experimental results, showed why no mixed crystals are formed from two or all three molecules. Data from the USAXS region suggested that, when using all three molecules, a more compact fractal structure was obtained, compared with those if one or two of the molecules were used.

Chemistry↗

Characterization of Submicron Bubbles Formed by the Hydrophobin Cerato-ulmin

Cerato-ulmin is a fungal hydrophobin protein with a high surface activity because of its amphipathic nature. When aqueous dispersions are gently agitated by hand, cerato-ulmin (CU) assembles into cylindrical bubbles visible in an optical microscope. After approximately 1 h the larger micron-sized bubbles rise out of the solution, leaving only submicron particulates, which persist indefinitely. Dynamic light scattering experiments show that these persistent particles shrink when positive air pressure is applied to the suspension and expand when vacuum is applied. Small-angle X-ray scattering at ambient pressure suggests an extended core–shell structure, consistent with small air-filled bubbles stabilized by a protein film. A comparison between the SAXS of the persistent submicron bubbles and AFM of the buoyant larger bubbles found immediately after agitation show that both have similar film thickness of 13–15 nm or five protein molecules. The extended shapes confirm the solid-like properties of these CU membranes, even in submicron particulate structures, consistent with microtensiometry results on interfacial CU membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗

ARPES-parameterized Hubbard approach to d-wave cuprate superconductors

In the last decade, the Angle Resolved Photoemission Spectroscopy (ARPES) has achieved important advances in both energy and angular resolutions, providing a direct measurement of the single-particle dispersion relation and superconducting gap. These dispersion relation data allow a full determination of the self-energy, first and second neighbor parameters in the Hubbard model. This model and its generalizations offer a simple and general way to describe the electronic correlation in solids. In particular, the parameters of correlated hopping interactions, responsible of the d-wave superconductivity in the generalized Hubbard model, are determined from ARPES data and the critical temperature within the mean-field approximation. In this work, we determine the model parameters for Bi{sub 2}Sr{sub 2−x}La{sub x}CuO{sub 6+δ} and study its d-wave superconducting gap as a function of temperature by solving numerically two coupled integral equations. Finally, the calculated electronic specific heat is compared with experimental results.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Highly mobile segments in crystalline poly(ethylene oxide){sub 8}:NaPF{sub 6} electrolytes studied by solid-state NMR spectroscopy

Two types of high-crystallinity poly(ethylene oxide)/NaPF{sub 6} electrolytes with ethylene oxide (EO)/Na molar ratios of 8:1 and 6:1, termed as PEO{sub 8}:NaPF{sub 6} and PEO{sub 6}:NaPF{sub 6} with M{sub w} = 6000 g mol{sup −1} were prepared, and their ionic conductivity, structure, and segmental motions were investigated and compared. PEO{sub 8}:NaPF{sub 6} polymer electrolyte exhibits the room-temperature ionic conductivity 7.7 × 10{sup −7} S cm{sup −1} which is about five times higher than the PEO{sub 6}:NaPF{sub 6}. By variable-temperature measurements of static powder spectra and {sup 1}H spin-lattice relaxation time in rotation frame ({sup 1}H T{sub 1ρ}), we demonstrate that crystalline segments are more highly mobile in the crystalline PEO{sub 8}:NaPF{sub 6} with higher ionic conductivity than in the PEO{sub 6}:NaPF{sub 6} with lower ionic conductivity. The large-angle reorientation motion of polymer segments in the PEO{sub 8}:NaPF{sub 6} onsets at lower temperature (∼233 K) with a low activation energy 0.31 eV that is comparable with that of the pure PEO crystal. Whereas, the large-angle reorientation motion of polymer segments in the PEO{sub 6}:NaPF{sub 6} starts around 313 K with a high activation energy of 0.91 eV. As a result of the temperature-enhanced large-angle reorientations, the {sup 13}C static powder lineshape changes markedly from a low-temperature wide pattern with apparent principal values of chemical shift δ{sub 33} < δ{sub 22} < δ{sub 11} to a high-temperature narrow pattern of uniaxial chemical shift anisotropy δ{sub 33} > δ{sub 22} (δ{sub 11}). It is suggested that the segmental motion in crystalline PEO-salt complex promotes ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗