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At least 127 records · Page 7

Supertwisted spirals of layered materials enabled by growth on non-Euclidean surfaces

Using curves to make twists The growth of layered materials on flat substrates usually occurs in stacked layers, although defects or a lattice mismatch can induce strains that distort the shape of subsequent layers. However, these effects are usually small and can be uncontrolled. Zhao et al. now demonstrate the possibility of synthesizing multilayers of two-dimensional materials with certain twists between the layers induced by the presence of screw dislocations in combination with curved substrate surfaces. Different twist angles are achieved by varying the amount of nonplanarity and the character (conical or hyperbolic) of the surface. Science , this issue p. 442

Science & Technology - Other Topics↗

Cloud, Aerosol and Boundary Layer Structure across the Northeast Pacific Stratocumulus-Cumulus Transition as observed during CSET

During the Cloud System Evolution in the Trades (CSET) field study, 14 research flights of the National Science Foundation G-V sampled the stratocumulus-cumulus transition between Northern California and Hawaii and its synoptic variability. The G-V made vertically resolved measurements of turbulence, cloud microphysics, aerosol characteristics, and trace gases. It also carried dropsondes and a vertically pointing W-band radar and lidar. This paper summarizes these observations with the goals of fostering novel comparisons with theory, models and reanalyses, and satellite-derived products. A longitude-height binning and compositing strategy mitigates limitations of sparse sampling and spatiotemporal variability. Typically, a 1-km-deep decoupled stratocumulus-capped boundary layer near California evolved into 2-km-deep precipitating cumulus clusters surrounded by patches of thin stratus that dissipated toward Hawaii. Low cloud cover was correlated with estimated inversion strength more than with cloud droplet number, even though the thickest clouds were generally precipitating and ultraclean layers indicative of aerosol-cloud-precipitation interaction were common west of 140 degrees W. Accumulation-mode aerosol concentration correlated well with collocated cloud droplet number concentration and was typically largest near the surface. Aitken mode aerosol concentration was typically larger in the free troposphere. Wildfire smoke produced spikes of aerosol and trace gases on some flights. CSET data are compared with space-time collocated output from MERRA-2 reanalysis and from the CAM6 climate model run with winds and temperature nudged toward this reanalysis. The reanalysis compares better with the observed relative humidity than does nudged CAM6. Both vertically diffuse the stratocumulus cloud layer versus observations. MERRA-2 slightly underestimates in situ carbon monoxide measurements and underestimates ozone depletion within the boundary layer.

Bretherton, Christopher S.↗

Microbeam X-Ray Absorption Near-Edge Spectroscopy of Alloying Elements in the Oxide Layers of Irradiated Zircaloy-2

Hydrogen pickup of zirconium-based fuel cladding and structural materials during in-reactor corrosion can degrade fuel components because the ingress of hydrogen can lead to the formation of brittle hydrides. In the boiling water reactor (BWR) environment, Zircaloy-2 fuel cladding and structural components such as water rods and channels can experience accelerated hydrogen pickup, whereas Zircaloy-4 components exposed to similar conditions do not. Because the principal difference between the two alloys is that Zircaloy-2 contains nickel, accelerated hydrogen pickup has been hypothesized to result from the presence of nickel. However, an understanding of the mechanism by which this acceleration occurs is still lacking. We investigated the link between hydrogen pickup and the oxidation behavior of alloying elements when incorporated into the oxide layers formed on zirconium alloys when corroded in the reactor. Synchrotron radiation microbeam X-ray absorption near-edge spectroscopy (XANES) at the Advanced Photon Source was performed on carefully selected BWR-corroded Zircaloy-2 water rods at an assembly-averaged burnup ranging from 32.8 to 74.6 GWd/MTU to determine the oxidation states of alloying elements, such as iron and nickel, within the oxide layers as a function of distance from the oxide-metal interface at high burnup. Samples were chosen for comparison based on having similar oxide thicknesses, processing, elevation, reactors, and fluences but different hydrogen pickup fractions. Examinations of the oxide layers formed on these samples showed that (1) the oxidation states of these alloying elements changed with distance from the oxide-metal interface, (2) these elements exhibited delayed oxidation relative to the host zirconium, and (3) nickel in Zircaloy-2 remained metallic in the oxide layer at a longer distance from the oxide-metal interface than iron. An analysis of these results showed an apparent correlation between the delayed oxidation of nickel and higher hydrogen pickup of Zircaloy-2 at high burnup.

alloying elements↗

Aircraft-derived particle fluxes distinguish entrainment zone and decoupled layer nucleation in marine boundary layers

The vertical distribution of freshly nucleated aerosol particles in the marine boundary layer remains poorly constrained, limiting our ability to represent new particle formation in climate models. Here we characterize 3–10 nm particle events, termed small particle events (SPEs), by deriving their vertical turbulent fluxes from aircraft measurements during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) campaign. To overcome stationarity limitations of traditional eddy covariance methods, we applied continuous wavelet transform analysis to data collected during June–July 2017 and January–February 2018 flights over the Azores. Our flux-based analysis revealed two distinct SPE scenarios with different vertical structures and spatial extents. The first featured nucleation in the entrainment zone, where free tropospheric air entrains into the boundary layer. The second showed nucleation in the decoupled layer, a stratified region between the well-mixed surface layer and cloud-topped upper boundary layer. In both cases, convergence of air masses from different layers diluted preexisting aerosol surface area to very low levels, creating conditions favorable for nucleation and generating strong downward particle fluxes. SPEs occurred in 15 % of flights, challenging prevailing theoretical expectations that new particle formation should rarely occur in marine boundary layers due to high condensation and coagulation sink capacity of sea spray aerosols. Aircraft-derived particle fluxes provide first observational constraints on the vertical location and source strength of likely nucleation regions in the remote marine boundary layer, improving aerosol source representations in climate models and reducing uncertainties in aerosol-cloud interactions.

Rasheeda Satheesh, Ajmal [North Carolina State Uni↗

Selective layer disordering in intersubband Al 0.028 Ga 0.972 N/AlN superlattices with silicon nitride capping layer

We demonstrate the selective layer disordering in intersubband Al 0.028 Ga 0.972 N/AlN superlattices using a silicon nitride (SiN x ) capping layer. The (SiN x ) capped superlattice exhibits suppressed layer disordering under high-temperature annealing. In addition, the rate of layer disordering is reduced with increased SiN x thickness. The layer disordering is caused by Si diffusion, and the SiN x layer inhibits vacancy formation at the crystal surface and ultimately, the movement of Al and Ga atoms across the heterointerfaces. In conclusion, patterning of the SiN x layer results in selective layer disordering, an attractive method to integrate active and passive III–nitride-based intersubband devices.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Modeling marine boundary-layer clouds with a two-layer model: A one-dimensional simulation

A two-layer model of the marine boundary layer is described. The model is used to simulate both stratocumulus and shallow cumulus clouds in downstream simulations. Over cold sea surfaces, the model predicts a relatively uniform structure in the boundary layer with 90%-100% cloud fraction. Over warm sea surfaces, the model predicts a relatively strong decoupled and conditionally unstable structure with a cloud fraction between 30% and 60%. A strong large-scale divergence considerably limits the height of the boundary layer and decreases relative humidity in the upper part of the cloud layer; thus, a low cloud fraction results. The efffects of drizzle on the boundary-layer structure and cloud fraction are also studied with downstream simulations. It is found that drizzle dries and stabilizes the cloud layer and tends to decouple the cloud from the subcloud layer. Consequently, solid stratocumulus clouds may break up and the cloud fraction may decrease because of drizzle.

Wang, Shouping↗

Accretion disk boundary layers in cataclysmic variables. 1: Optically thick boundary layers

We develop numerical models of accretions disks in cataclysmic variables (CVs), including and emphasizing the boundary layer region where the accretion disk meets the accreting white dwarf. We confine ourselves to solutions where the boundary layer region is vertically optically thick, and find that these solutions share several common features. The angular and radial velocities of the accreting material drop rapidly in a dynamical boundary layer, which has a radial width approximately 1%-3% of the white dwarf radius. The energy dissipated in this region diffuses through the inner part of the disk and is radiated from the disk surface in a thermal boundary layer, which has a radial width comparable to the disk thickness, approximately 5%-15% of the white dwarf radius. We examine the dependence of the boundary layer structure on the mass accretion rate, the white dwarf mass and rotation rate, and the viscosity parameter alpha. We delineate the boundary between optically thick and optically thin boundary layer solutions as a function of these parameters and suggest that by means of a careful comparison with observations it may be possible to estimate alpha in CVs. We derive an expression for the total boundary layer luminosities as a function of the parameters and show that it agrees well with the luminosites of our numerical solutions. Finally, we calcuate simple blackbody continuum spectra of the boundary layer and disk emission for our solutions and compare these to soft X-ray, EUV, and He II emission-line observations of CVs. We show that, through such comparisons, it may be possible to determine the rotation rates of the accreting stars in CVs, and perhaps also the white dwarf masses and the accretion rates. The spectra are quite insensitive to alpha, so the uncertainty in this parameter does not affect such comparisons.

Popham, Robert↗

Artificial Thickening of a Transonic Boundary Layer in the Presence of a Pressure Gradient Associated with a Boundary Layer Ingestion Concept

Boundary layer ingestion is an aeropropulsive concept associated with a propulsion airframe integration technique that integrates viscous aerodynamics into a propulsion system to achieve more efficient flight. The effectiveness of this concept is heavily dependent on how much of the boundary layer is being ingested into the propulsor. Scaling this concept for transonic wind tunnel testing is often plagued with blockage issues and requires a modification to the model dimensions such as fuselage length and diameter and wingspan. To simulate the boundary layer for these modified models requires a manipulation of the boundary layer height to achieve the appropriate ratio of boundary layer to propulsor inlet diameter or height. This paper will focus on 15 different transonic boundary layer manipulators to achieve varying turbulent boundary layer heights for a representative single-aisle transport utilizing Boundary Layer Ingestion.

Gregory S Jones↗

Origin, nature, and the dynamic behavior of nanoscale vacancy clusters in Ni-rich layered oxide cathodes

Oxygen and transition metal (TM) vacancies in transition metal oxides (TMOs) play an important role in materials functionalities. For TMO cathodes of Li-ion batteries, vacancies can be introduced, either deliberately or inevitably, during materials synthesis or upon electrochemical cycling. Effects of vacancies on the electrochemical properties of cathodes critically depend on the dynamic characteristics of vacancies during the battery cycling. However, a fundamental understanding of such characteristics in the layer structured cathode remains elusive. Here, using scanning transmission electron microscopy (STEM), we reveal a cycling-induced aggregation behavior of oxygen and TM vacancies in a Ni-rich layer structured cathode of secondary particles. We discover that during the initial charging, vacancies aggregate to form visible vacancy-rich nanoregions (vacancy clusters) firstly at the outer layer of the secondary particle, and then the vacancy-cluster populated region extends to the inner part of particle upon fully charged. The spatial distinction of preferential nucleation of vacancy clusters at the outer layer indicates that the vacancy migration and clustering is associated with Li migration flux, which is larger at the outer layer, as all the Li from the inner part has to go through the outer layer. With extended cycling (> 50), these vacancy clusters become immobilized. We further reveal that the generation of these vacancy clusters is correlated to the material-synthesis conditions. Our findings solve a long-standing puzzle on the origin, nature, and behavior of the commonly visible vacancy clusters in the NMC cathode, providing insights on correlation between properties and dynamic behaviors of atomic-scale defects in layered oxide cathodes.

Li-ion batteries, layered oxide cathodes, NMC, cat↗

Two-Dimensional Layered Oxide Structures Tailored by Self-Assembled Layer Stacking via Interfacial Strain

Two-dimensional (2D) nanostructures emerge as one of leading topics in fundamental materials science and could enable next generation nanoelectronic devices. Beyond graphene and molybdenum disulphide, layered complex oxides are another large group of promising 2D candidates because of their strong interplay of intrinsic charge, spin, orbital and lattice. As a fundamental basis of heteroepitaxial thin film growth, interfacial strain can be used to design materials exhibiting new phenomena beyond their conventional form. Here we report the strain-driven self-assembly of Bismuth-based supercells (SC) with a 2D layered structure, and elucidate the fundamental growth mechanism with combined experimental tools and first-principles calculations. The study revealed that the new layered structures were formed by the strain-enabled self-assembled atomic layer stacking, i.e., alternative growth of Bi 2 O 2 layer and [Fe 0.5 Mn 0.5 ]O 6 layer. The strain-driven approach is further demonstrated in other SC candidate systems with promising room-temperature multiferroic properties. This well-integrated theoretical and experimental study inspired by the Materials Genome Initiatives opens up a new avenue in searching and designing novel 2D layered complex oxides with enormous promises.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Clusters, molecular layers, and 3D crystals of water on Ni(111)

We examined the growth and stability of ice layers on Ni(111) up to ∼7 molecular layers (ML) thick using scanning tunneling microscopy. At low coverage, films were comprised of ∼1 nm wide two-dimensional (2D) clusters. Only above ∼0.5 ML did patches of continuous 2D layers emerge, coexisting with the clusters until the first ML was complete. The structure of the continuous layer is clearly different from that of the 2D clusters. Subsequently, a second molecular layer grew on top of the first. 3D crystallites started to form only after this 2nd ML was complete. 2D clusters re-appeared when thicker films were partially evaporated, implying that these clusters represent the equilibrium configuration at low coverage. Binding energies and image simulations computed with density functional theory suggest that the 2D clusters are partially dissociated and surrounded by H adatoms. The complete 2D layer contains only intact water molecules because of the lack of favorable binding sites for H atoms. We propose molecular structures for the 2D layer that are composed of the same pentagon-heptagon binding motif and water density observed on Pt(111). The similarity of the water structures on Pt and Ni suggests a general prescription for generating low-energy configurations on close-packed metal substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic-scale Mechanisms of Enhanced Electrochemical Properties of Mo-doped Co-free Layered Oxide Cathodes for Lithium-Ion Batteries

Cobalt-free layered oxides with high specific capacity and low cost have emerged as promising candidates for next-generation cathodes for lithium-ion batteries. However, implementation of these materials has been hindered by their low rate capability, structural instability, and rapid capacity decay during cycling. Recent studies have shown that introducing cation dopants into layered oxides can strongly improve their electrochemical properties, but the underlying mechanisms remain elusive due to a lack of information at the atomic scale. In this work, we use a combination of atomic-resolution scanning transmission electron microscopy and first principle calculations to reveal the microscopic origin of enhanced electrochemical properties in LiNi0.5Mn0.5O2 doped with ~1 at % Mo. These results indicate that the Mo dopant hinders Li+/Ni2+ cation mixing and suppresses detrimental phase transformations near the particle surface and at grain boundaries, which enhances the cathode’s reversible capacity and cycling stability. Overall, This work provides important insights on how cation doping affects the structure and electrochemical properties of layered oxide cathodes.

Li, Linze↗

Surface Reordering During Layer‐by‐Layer Growth on SrTiO 3

With the development of layer‐by‐layer growth techniques such as molecular beam epitaxy (MBE), it is now possible to construct materials with atomic‐level precision, with the layer sequence primarily determined by the growth recipe. However, materials can still restructure in the high‐temperature growth environment with surface thermodynamics strongly influencing growth behavior. Here, we demonstrate that growth on ${\rm SrTiO}_{3}$ (001), the principal platform for oxide electronics, does not occur in a layer‐by‐layer fashion but follows a more complex process in which a ${\rm TiO}_{2}$ plane continually diffuses toward the growth surface. Employing in situ synchrotron X‐ray scattering combined with ab initio thermodynamic calculations, we discover the existence of a stable ${\rm TiO}_{2}$ double‐layer structure on the pristine substrate and the occurrence of dynamic layer rearrangement during homoepitaxial growth by oxide MBE. Our findings suggest that the current methods used to precisely control ${\rm SrTiO}_{3}$ surfaces are limited, as well as our ability to dictate the composition of ultrathin films, resulting in important ramifications regarding the surface reactivity of perovskite materials grown on ${\rm SrTiO}_{3}$.

Coherent Bragg Rod Analysis↗

A trifunctional multi-walled carbon nanotubes/polyethylene glycol (MWCNT/PEG)-coated separator through a layer-by-layer coating strategy for high-energy Li–S batteries

In this study, a trifunctional separator fabricated by using a light-weight layer-by-layer multi-walled carbon nanotubes/polyethylene glycol (MWCNT/PEG) coating has been explored in lithium–sulfur (Li–S) batteries. The conductive MWCNT/PEG coating serves as (i) an upper current collector for accelerating the electron transport and benefiting the electrochemical reaction kinetics of the cell, (ii) a net-like filter for blocking and intercepting the migrating polysulfides through a synergistic effect including physical and chemical interactions, and (iii) a layered barrier for inhibiting the continuous diffusion and alleviating the volume change of the trapped active material by introducing a “buffer zone” in between the coated layers. The multi-layered MWCNT/PEG coating allows the use of the conventional pure sulfur cathode with a high sulfur content (78 wt%) and high sulfur loading (up to 6.5 mg cm -2 ) to achieve a high initial discharge capacity of 1206 mA h g -1 at C/5 rate, retaining a superior capacity of 630 mA h g -1 after 300 cycles. Lastly, the MWCNT/PEG-coated separator optimized by the facile layer-by-layer coating method provides a promising and feasible option for advanced Li–S batteries with high energy density.

25 ENERGY STORAGE↗

Layer-by-layer growth of graphene oxide multilayers using robust interlayer linking chemistry. 1. Zr-bisphosphates

Graphene oxide (GO) holds substantial interest because of its utility in applications ranging from chemical sensing to catalysis and energy storage. We report on the layer-by-layer formation of graphene oxide phosphate (P-GO) multilayers on silica and oxidized silicon supports, with the layers connected via Zr-bisphosphate (ZP) linking chemistry. Layers were grown either directly by ZP linkages between P-GO sheets, or with the use of 1,4-phenylene bisphosphate (BP1) or [1,1′-biphenyl]4,4′-diyl bisphosphate (BP2). The layers have been characterized using optical null ellipsometry, X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy and scanning electron microscopy (SEM). There is a linear dependence of assembly thickness on the number of layers deposited and the integrated area of the optical absorbance bands also increases linearly with number of layers deposited. XPS data provides information on interlayer linking stoichiometry. SEM images provide insight into the morphology of the adlayers, suggesting the structure and length of the interlayer linking moieties used in the multilayer assembly play a significant role in the organization of the resulting system.

Mukherjee, Neelanjana [Michigan State University, ↗

Electron-stimulated reactions in layered CO/H{sub 2}O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

Low-energy (100 eV) electron-stimulated reactions in layered H{sub 2}O/CO/H{sub 2}O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H{sub 2}O and D{sub 2}O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic pinning in a superconducting film by a ferromagnetic layer with stripe domains

A magnetic study of superconductor/ferromagnet bilayers was performed by hysteresis loops and temperature-dependent magnetization measurements. The superconductor/ferromagnet bilayers consist of a Nb film deposited on a Py film with weak perpendicular magnetic anisotropy. By comparing the temperature-dependent magnetization data obtained on samples with different ferromagnetic layer thickness, a decrease of the magnetic pinning with increasing thickness of the ferromagnetic layer has been found. This is confirmed by the reduction of the Nb film critical current density at low fields extracted by using the magnetic irreversibility of the hysteresis loops. Here, the reduction of the pinning can be related to the increase of the stripe width in the ferromagnetic layer observed by magnetic force microscopy (MFM) measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗