Long-Range and Short-Range Structures of Multimetallic Layered Double Hydroxides
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One-dimensional kagome strip chains share much of the same frustrated structural motif as two-dimensional kagome antiferromagnets, making them valuable for deepening our understanding of kagome lattice magnetism. In this paper, we report the hydrothermal synthesis and detailed structural and property characterization of Na 2 Co 3 (AsO 4 ) 2 (OH) 2 , a striped kagome system. The crystal structure was characterized using single crystal X-ray diffraction which reveals that Na 2 Co 3 (AsO 4 ) 2 (OH) 2 crystallizes in monoclinic crystal system C2/m. The structure features a one-dimensional kagome strip lattice built from Co 2+ ions and undergoes an antiferromagnetic transition at T N = 14 K. The magnetic ground state at zero field was characterized using neutron powder diffraction. Below the magnetic transition, Na 2 Co 3 (AsO 4 ) 2 (OH) 2 orders into an antiferromagnetic structure with a k-vector (0.5, 0.5, 0.5). In the proposed model, the Co1 moment is predominantly confined to the ac-plane while the Co2 moment is primarily aligned along the b-axis. Two flat bands were observed in the inelastic neutron spectra below the magnetic transition, 5 and 10 meV. Inelastic neutron spectra were modeled with a Heisenberg Hamiltonian including three nearest-neighbor exchange interactions (J 1 , J 2 , J 3 ) and strong single-ion anisotropy to stabilize the observed magnetic structure. Our study highlights the complexity of Co 2+ -based kagome strip magnetic lattice compound Na 2 Co 3 (AsO 4 ) 2 (OH) 2 which provides an excellent platform to broaden our understanding of the frustrated kagome magnetic lattice space.
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Program handles segmented, laminar, orthotropic shells with discrete rings. Meridional variations are handled in material properties, temperatures, and wall thickness. Allows for linear variations of temperature through each layer of shell wall.
Results of multiple-scattering computations based on whole-disk and Digicon polarization observations are presented which indicate vertical inhomogeneity in the upper atmosphere of Venus. It is shown that the whole-disk observations support a thin upper haze layer of 0.18-micron particles and that the low polarization observed near the limb and terminator requires a haze of slightly larger particles. The Digicon polar regions are found to exhibit increased polarization, which is compatible with CO2 absorption measurements and is explained by increased molecular scattering above the clouds. The decrease in cloud-top height for latitudes greater than 45 deg is estimated to be approximately 1.4 km.
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A perturbation scheme, based on the simultaneous expansion of primary and secondary modes, is used to study the prebreakdown flow field. Results of the analysis are in good agreement with experiments for amplitudes in excess of 5 percent. For peak-valley splitting, the analysis captures the development of the high shear layer associated with breakdown. Subharmonic modes evolve differently, with the region of high shear concentrated near the wall.
We present comparisons of cloud droplet size distributions (DSDs) retrieved from the research scanning polarimeter (RSP) data with correlative in situ measurements made during the North Atlantic Aerosols and Marine Ecosystems Study (NAAMES). The airborne portion of this field experiment was based out of St. John's airport, Newfoundland, Canada with the focus of this paper being on the deployment in May - June 2016. RSP was onboard the NASA C-130 aircraft together with an array of in situ and other remote sensing instrumentation. The RSP is an along-track scanner measuring the polarized and total reflectance in 9 spectral channels. Its uniquely high angular resolution allows for characterization of liquid water droplet sizes using the rainbow structure observed in the polarized reflectance over the scattering angle range from 135 to 165.degrees The rainbow is dominated by single scattering of light by cloud droplets, so its structure is characteristic specifically of the droplet sizes at cloud top (within unit optical depth into the cloud, equivalent to approximately 50m). A parametric fitting algorithm applied to the polarized reflectance provides retrievals of the droplet effective radius and variance assuming a prescribed size distribution shape (gamma distribution). In addition to this, we use a non-parametric method, the Rainbow Fourier Transform (RFT), which allows us to retrieve the droplet size distribution itself. The latter is important in the case of clouds with complex microphysical structure, or multiple layers of cloud, which result in multi-modal DSDs. During NAAMES the aircraft performed a number of flight patterns specifically designed for comparisons between remote sensing retrievals and in situ measurements. These patterns consisted of two flight segments above the same straight ground track. One of these segments was flown above clouds allowing for remote sensing measurements, while the other was near the cloud top where cloud droplets were sampled. We compare the DSDs retrieved from the RSP data with in situ measurements made by the Cloud Droplet Probe (CDP). The comparisons generally show good agreement (better than 1 micron for effective radius and in most cases better than 0.02 for effective variance) with deviations explainable by the position of the aircraft within the cloud, or by the presence of additional cloud layers between the cloud being sampled by the in situ instrumentation and the altitude of the remote sensing segment. In the latter case, the multi-modal DSDs retrieved from the RSP data were consistent with the multi-layer cloud structures observed in the correlative High Spectral Resolution Lidar (HSRL) profiles. The results of these comparisons provide a rare validation of polarimetric droplet size retrieval techniques, demonstrating their accuracy and robustness and the potential of satellite data of this kind on a global scale.
The occurrence of large-scale coherent structures in turbulent free shear flows (especially the planar mixing layer) has been recognized for some time. Indeed, the observation of such structures in mixing layers did much to promote interest in the study of coherent structures in turbulence. It has been widely assumed that the large-scale structures in these flows are responsible for the entrainment of free-stream fluid and the overall growth of the layer, while the small-scale structures provide mixing and dissipation. A model of scalar mixing based on these ideas was proposed for these flows. However, recent experimental and computational evidence suggests that the dominance of the large-scale structures in turbulent mixing layers is not universal. In addition, there is a substantial variation among experiments in several statistical measures of self-similar mixing layers, for example growth rate and velocity variances. To investigate the importance of large-scale structures, several free shear flows (mixing layers and wakes) have been simulated via direct numerical simulation. The simulations are designed to mimic experimental mixing layers in which the splitter plate boundary layers are turbulent. Different levels of two-dimensional forcing are included resulting in large-scale structures of differing strength and importance. These simulations are used to investigate the role of large-scale coherent structures in free shear layers and the effect of these structures on relevant turbulence statistics and scalar mixing. It is found that the statistics and structures in several experiments involving turbulent mixing layers are in better agreement with simulations that do not exhibit dominant large-scale structures than those in which the common mixing layer structures do dominate. It is also found that the level of forcing can have a profound effect on the qualitative and quantitative features of these shear layer, even when they are nominally self-similar.
The structural and morphological characteristics of visible-light-emitting porous Si layers produced by anodic and stain etching of single-crystal Si substrates are compared using transmission electron microscopy and atomic force microscopy (AFM). AFM of conventionally anodized, laterally anodized and stain-etched Si layers show that the layers have a fractal-type surface morphology. The anodized layers are rougher than the stain-etched films. At higher magnification 10 nm sized hillocks are visible on the surface. Transmission electron diffraction patterns indicate an amorphous structure with no evidence for the presence of crystalline Si in the near-surface regions of the porous Si layers.
The three-dimensional turbulent boundary layer is shown to have a self-consistent two-layer asymptotic structure in the limit of large Reynolds number. In a streamline coordinate system, the streamwise velocity distribution is similar to that in two-dimensional flows, having a defect-function form in the outer layer which is adjusted to zero at the wall through an inner wall layer. An asymptotic expansion accurate to two orders is required for the cross-stream velocity which is shown to exhibit a logarithmic form in the overlap region. The inner wall-layer flow is collateral to leading order but the influence of the pressure gradient, at large but finite Reynolds numbers, is not negligible and can cause substantial skewing of the velocity profile near the wall. Conditions under which the boundary layer achieves self-similarity and the governing set of ordinary differential equations for the outer layer are derived. The calculated solution of these equations is matched asymptotically to an inner wall-layer solution and the composite profiles so formed describe the flow throughout the entire boundary layer. The effects of Reynolds number and cross-stream pressure gradient on the crossstream velocity profile are discussed and it is shown that the location of the maximum cross-stream velocity is within the overlap region.
Report describes experimental study of three-dimensional structure of nominally planar two-stream mixing layer. Purpose of study, to obtain quantitative data on evolution of streamwise vortexes.
The underlying premise in this work is that large structures in turbulent shear flows are not universal and similar large structures in different flows owe their origins to basically similar instabilities. The turbulent boundary-layer flow over a backward-facing step and also the reattaching transitional boundary layer behind a large spanwise rod have been studied experimentally in parallel primarily to understand the origin of the curious large structures observed in the far downstream region (after 39 step heights) of the former flowfield. Simultaneous flow visualization and hot-wire anemometry and also plain-flow visualization have been carried out. In the backward-facing step, the three-dimensional mixing layer developing after detachment persists even after reattachment. The flow does not recover fully back to a regular turbulent boundary layer even far downstream of reattachment. The turbulence-producing instability of a turbulent boundary layer continues to compete with the wall-bounded mixing layer instability, giving rise to the curious schismatic arrays of large structures.
Abstract Layered lithium transition‐metal oxide materials, e.g., Li(Ni 1− x − y Co x Mn y )O 2 (NCM) and Li(Ni 1− x − y Co x Al y )O 2 , are the most promising candidates for lithium‐ion battery cathodes. They generally consist of ≈10 µm spherical particles densely packed with smaller particles (0.1–1 µm), called secondary and primary particles, respectively. The micrometer‐ to nanometer‐sized particles are critical to the battery performance because they affect the reaction capability of the cathode. Herein, the crystal structure of the primary particles of NCM materials is revisited. Elaborate transmission electron microscopy investigations reveal that the so‐called primary particles, often considered as single crystals, are in fact polycrystalline secondary particles. They contain low‐angle and exceptionally stable special grain boundaries (GBs) presumably created during aggregation via an oriented attachment mechanism. Therefore, this so‐called primary particle is renamed as primary‐like particle. More importantly, the low‐angle GBs between the smaller true primary particles cause the development of nanocracks within the primary‐like particles of Ni‐rich NCM cathodes after repetitive electrochemical cycles. In addition to rectifying a prevalent misconception about primary particles, this study provides a previously unknown but important origin of structural degradation in Ni‐rich layered cathodes.
Spanwise structures of 'nominally' two-dimensional (2D), spatially growing, turbulent mixing layers are simulated numerically by a three-dimensional (3D) vortex method. Small-amplitude 3D disturbances are introduced into an otherwise 2D flow field. Results show that a large-scale spanwise variation of the flow field is produced because of amplification of initial disturbances. Pairs of counterrotating streamwise vortices are formed as a result of stretching of primary spanwise vortices. The streamwise vortices are formed at a fixed spanwise location which depends on initial disturbances. The calculated magnitude of streamwise vorticity is close to that of the spanwise vorticity. The results also suggest that the presence of background disturbances may be essential for the formation of streamwise vortices. The results are in good qualitative agreement with experiments.
The emergence of layered sodium transition metal oxides featuring a multiphase structure presents a promising approach for cathode materials in sodium-ion batteries, showcasing notably improved energy storage capacity. However, the advancement of cathodes with multiphase structures faces obstacles due to the limited understanding of the integrated structural effects. Herein, the integrated structural effects by an in-depth structure-chemistry analysis in the developed layered cathode system Na x Cu 0.1 Co 0.1 Ni 0.25 Mn 0.4 Ti 0.15 O 2 with purposely designed P2/O3 phase integration, are comprehended. The results affirm that integrated phase ratio plays a pivotal role in electrochemical/structural stability, particularly at high voltage and with the incorporation of anionic redox. In contrast to previous reports advocating solely for the enhanced electrochemical performance in biphasic structures, it is demonstrated that an inappropriate composite structure is more destructive than a single-phase design. The in situ X-ray diffraction results, coupled with density functional theory computations further confirm that the biphasic structure with P2:O3 = 4:6 shows suppressed irreversible phase transition at high desodiated states and thus exhibits optimized electrochemical performance. Finally, these fundamental discoveries provide clues to the design of high-performance layered oxide cathodes for next-generation SIBs.