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At least 217 records · Page 12

Unblocking Oxygen Charge Compensation for Stabilized High‐Voltage Structure in P2‐Type Sodium‐Ion Cathode

Abstract Layered transition‐metal (TM) oxides are ideal hosts for Li + charge carriers largely due to the occurrence of oxygen charge compensation that stabilizes the layered structure at high voltage. Hence, enabling charge compensation in sodium layered oxides is a fascinating task for extending the cycle life of sodium‐ion batteries. Herein a Ti/Mg co‐doping strategy for a model P2‐Na 2/3 Ni 1/3 Mn 2/3 O 2 cathode material is put forward to activate charge compensation through highly hybridized O 2 p TM 3 d covalent bonds. In this way, the interlayer OO electrostatic repulsion is weakened upon deeply charging, which strongly affects the systematic total energy that transforms the striking P2–O2 interlayer contraction into a moderate solid‐solution‐type evolution. Accordingly, the cycling stability of the codoped cathode material is improved superiorly over the pristine sample. This study starts a perspective way of optimizing the sodium layered cathodes by rational structural design coupling electrochemical reactions, which can be extended to widespread battery researches.

25 ENERGY STORAGE↗

Design and Characterization of Hybrid Multilayer Structures: Layer-by-Layer Growth of Polymer and Graphene Oxide Assemblies and Their Utility in Fuel Cell Applications

We report the layer-by-layer growth of poly- (ethylenimine) (PEI) that has been modified with sulfamate functionalities (S-PEI) using Zr 4+ -complexation interlayer linking chemistry. We have also deposited adlayers of graphene oxide (GO) that have been modified to possess sulfate functionalities (SGO), onto the S-PEI layers. The multilayer assemblies are formed with sulfamate/sulfate and sulfate/sulfate (S-PEI + S-GO) interlayer linking chemistry. In all cases the adlayer thickness is consistent with predictions based on van der Waals volume and/or molecular mechanics calculations. X-ray photoelectron spectroscopy (XPS) is used to characterize the Zr/S stoichiometry in the multilayer assembly. The utility of these hybrid multilayer structures is demonstrated in a Proton Exchange Membrane (PEM) fuel cell, where they are shown to reduce H 2 gas crossover by 15% with only a 12 nm thick layer.

fuel cell↗

Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery

Solid-electrolyte interphase (SEI) is a key component that dictates the performance of most electrochemical devices, but the understanding of its chemistry and structure has been limited by the lack of in-situ tools. In this work, we report SEI live-formation in Li-ion battery under operando condition with liquid secondary ion mass spectrometry (SIMS), which, in combination with molecular dynamics (MD) simulation, presents the first dynamic picture with molecular-accuracy about this key component. Before any interphasial chemistry occurs during the initial charging, an electric double layer forms at the electrode-electrolyte interface via the self-assembly of solvent molecules directed by both Li+ and potential of the electrified surface. Such double layer structure predicts the eventual interphasial chemistries formed from the electrolytes, where the negatively-charged electrode surface repels salt anions from the inner-Helmholtz layer and results in an inner SEI that is thin, dense and inorganic in nature but LiF-depleted. It was this dense layer that exercises the major functions of an interphase, i.e., conducting Li+ but insulating electrons. An outer layer that is electrolyte-permeable and organic-rich appears after formation of the inner SEI. In highly-concentrated electrolyte, the presence of LiF in the inner-SEI is raised due to the high population of salt anions in the double layer. These real-time observations at nano-scale reveal in general sense how an interphase inherits chemistry from inner-Helmholtz layer structure, and establish guidelines in engineering desirable interphases for the future battery chemistries.

Zhou, Yufan↗

Persistent Structures in the Turbulent Boundary Layer

Persistent structures in the turbulent boundary layer are located and analyzed. The data are taken from flight experiments on large commercial aircraft. An interval correlation technique is introduced which is able to locate the structures. The Morlet continuous wavelet is shown to not only locates persistent structures but has the added benefit that the pressure data are decomposed in time and frequency. To better understand how power is apportioned among these structures, a discrete Coiflet wavelet is used to decompose the pressure data into orthogonal frequency bands. Results indicate that some structures persist a great deal longer in the TBL than would be expected. These structure contain significant power and may be a primary source of vibration energy in the airframe.

Palumbo, Dan↗

Integration of satellite and surface data using a radiative-convective oceanic boundary-layer model

A mixing-line boundary-layer model is used to retrieve cloud-top height from satellite-derived cloud-top temperatures, using 700-hPa National Meteorological Center (NMC) analyses and the Comprehensive Ocean and Atmosphere Data Set (COADS) surface data as supporting datasets. Results are compared with the fixed-lapse-rate method of retrieving boundary-layer depth from sea surface temperatures (SST) and cloud-top temperatures. A radiative-convective equilibrium boundary-layer model is used to retrieve boundary-layer structure given SST and surface wind, satellite cloud-top temperatures and cloud fraction, and the 700-hPa NMC thermodynamic analyses. Good agreement is found between the COADS data and the model solutions for low-level temperature and moisture. This suggests that equilibrium boundary-layer models may be of use over remote oceans in the retrieval of boundary-layer structure.

Betts, Alan K.↗

Special Features of the Structure of Titanium Nitride Coatings in Substrate Surface Cuts

Elemental compositions and structure-phase states of titanium nitride coatings on the flat surface and in a cut of substrate from 10Cr18Ni10Ti steel are investigated by the methods of x-ray microspectral analysis, Auger electron spectroscopy, and dark-field electron microscopy analysis of the bending-torsion of the crystal lattice. It is established that the coating in the cut, unlike the coating on the frontal surface, has a modified elemental composition and a two-layer structure whose special features and thicknesses change with distance from the sample surface. It is shown that these changes are caused by phase transformations, decreased number of defects, dispersion of layer structures, and increased concentration of impurities with increasing distance from the substrate surface. Based on the results obtained, possible conditions for coating structure formation in the cut of the substrate surface are discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mixed Layers and Satellite Retrievals

As part of the process to determine whether it is possible to retrieve boundary layer structure with the current sounding techniques, temperature retievals were performed for radiosonde profiles that showed temperature inversions. It was found that when temperature inversions exceed 8 to 10 C a retrieval will indeed show a temperature increase with height over a limited vertical distance. For weaker inversions retrieved temperatures are generally smoothly decreasing with height. It is, however, impossible to determine the actual mixed layer height from the retrievals. Whether the water vapor channels could be used in observing mixed layer structure was investigated. Temperature inversions are accompanied by significant drops in relative humidity. While this effect is very pronounced in parts of the trade wind regimes with relative humidity drops of up to 60%, it is widespread in other areas of the ocean as well. A simulation experiment was performed in which brightness temperatures were computed for smooth temperature and humidity profiles and compared with those computed from inversion profiles.

Boers, R.↗

Finite-rate chemistry effects upon convective and radiative heating of an atmospheric entry vehicle

A mathematical model of the aerothermochemical environment along the stagnation line of a planetary return spacecraft using an ablative thermal protection system was developed and solved for conditions typical of atmospheric entry from planetary missions. The model, implemented as a FORTRAN 4 computer program, was designed to predict viscous, reactive and radiative coupled shock layer structure and the resulting body heating rates. The analysis includes flow field coupling with the ablator surface, binary diffusion, coupled line and continuum radiative and equilibrium or finite rate chemistry effects. The gas model used includes thermodynamic, transport, kinetic and radiative properties of air and ablation product species, including 19 chemical species and 16 chemical reactions. Specifically, the impact of nonequilibrium chemistry effects upon stagnation line shock layer structure and body heating rates was investigated.

Guillermo, P.↗

Shear deformation plate continua of large double layered space structures

A simple method is presented to model large rigid-jointed lattice structures as continuous elastic media with couple stresses using energy equivalence. In the analysis, the transition from the discrete system to the continuous media is achieved by expanding the displacements and the rotations of the nodal points in a Taylor series about a suitable chosen origin. The strain energy of the continuous media with couple stresses is then specialized to obtain shear deformation plate continua. Equivalent continua for single layered grids, double layered grids, and three-dimensional lattices are then obtained.

Hefzy, Mohamed Samir↗

Atmospheric Layers Measured from the NASA DC-8 During PEM-West B and Comparison with PEM-West A

The Pacific Exploratory Mission-West B (PEM-West B) explored atmospheric layer structure using measurements of O3, H2O, CO, and CH4 from the NASA DC-8 fast-response instruments. The mission took place in February-March 1994 over the western Pacific, mainly in the northern hemisphere. Results were compared with similar measurements made during the Pacific Exploratory Mission-West A (PEM-West A) in September-October 1991. PEM-West B sampled 94 vertical profiles, with an average atmospheric depth per profile of 6.4 km, and this sampling yielded 254 discrete layers. PEM-West A sampled 105 profiles, also with a 6.4 km average depth, yielding 538 layers. Both missions revealed that layers containing high ozone and low water vapor were the most abundant, and low ozone and high water vapor layers were the next most abundant. Lidar images and potential vorticity cross sections showed the former associated with subsidence from the stratosphere in middle latitudes, spreading into the tropics. The latter was associated with convection from the boundary layer. The partition among different types of layers only changed slightly in the two missions, although PEM-West B had half as many layers. Compared to PEM-West A, PEM-West B showed only one-third the number of layers associated with polluted continental air. However, PEM-West B revealed significantly more layers showing characteristics of descended clean marine air. In some cases these layers originated from the southern hemisphere. For ozone- and water-vapor-rich layers, the ozone deviation amplitude was higher in low latitudes and lower in high latitudes in PEM-West B. The mean thickness of layers increased from about 450 m in PEM-West A to 680 in in PEM-West B. Layers also existed in the Intertropical Convergence Zone. CO2 measurements had sufficient vertical resolution to show layer structure as well.

Wu, Zhongxiang↗

The Estimation of Surface Latent Heat Flux over the Ocean and its Relationship to Marine Atmospheric Boundary Layer (MABL) Structure

A new technique combining active and passive remote sensing instruments for the estimation of surface latent heat flux over the ocean is presented. This synergistic method utilizes aerosol lidar backscatter data, multi-channel infrared radiometer data, and microwave scatterometer data acquired onboard the NASA P-313 research aircraft during an extended field campaign over the Atlantic ocean in support of the Lidar In-space Technology Experiment (LITE) in September of 1994. The 10 meter wind speed derived from scatterometers and lidar-radiometer inferred near-surface moisture are used to obtain an estimate of the surface flux of moisture via a bulk aerodynamic formula. The results are compared with the Special Sensor Microwave Imager (SSM/I) daily average latent heat flux and show reasonable agreement. However, the SSM/I values are biased low by about 15 W/sq m. In addition, the Marine Atmospheric Boundary Layer (MABL) height, entrainment zone thickness and integrated lidar backscatter intensity are computed from the lidar data and compared with the magnitude of the surface fluxes. The results show that the surface latent heat flux is most strongly correlated with entrainment zone depth, MABL height and the integrated MABL lidar backscatter, with corresponding correlation coefficients of 0.39, 0.43 and 0.71, respectively.

Palm, Stephen P.↗

Machine Learning for Improving Surface-Layer-Flux Estimates

Abstract Flows in the atmospheric boundary layer are turbulent, characterized by a large Reynolds number, the existence of a roughness sublayer and the absence of a well-defined viscous layer. Exchanges with the surface are therefore dominated by turbulent fluxes. In numerical models for atmospheric flows, turbulent fluxes must be specified at the surface; however, surface fluxes are not known a priori and therefore must be parametrized. Atmospheric flow models, including global circulation, limited area models, and large-eddy simulation, employ Monin–Obukhov similarity theory (MOST) to parametrize surface fluxes. The MOST approach is a semi-empirical formulation that accounts for atmospheric stability effects through universal stability functions. The stability functions are determined based on limited observations using simple regression as a function of the non-dimensional stability parameter representing a ratio of distance from the surface and the Obukhov length scale (Obukhov in Trudy Inst Theor Geofiz AN SSSR 1:95–115, 1946), $$z/L$$ z / L . However, simple regression cannot capture the relationship between governing parameters and surface-layer structure under the wide range of conditions to which MOST is commonly applied. We therefore develop, train, and test two machine-learning models, an artificial neural network (ANN) and random forest (RF), to estimate surface fluxes of momentum, sensible heat, and moisture based on surface and near-surface observations. To train and test these machine-learning algorithms, we use several years of observations from the Cabauw mast in the Netherlands and from the National Oceanic and Atmospheric Administration’s Field Research Division tower in Idaho. The RF and ANN models outperform MOST. Even when we train the RF and ANN on one set of data and apply them to the second set, they provide more accurate estimates of all of the fluxes compared to MOST. Estimates of sensible heat and moisture fluxes are significantly improved, and model interpretability techniques highlight the logical physical relationships we expect in surface-layer processes.

Meteorology & Atmospheric Sciences↗

A New Method for Polishing Laminated Dissimilar Metals

Here, this paper presents a novel method for preparing metallographic samples of laminated dissimilar metals, specifically a layered structure of zirconium (Zr), vanadium (V), and tungsten (W), which pose a challenge due to their differing crystal structures and hardness levels. The work was motivated by the need to develop a cladding for tungsten targets in spallation neutron sources, where a zirconium face is applied over an interlayer of either vanadium or titanium to prevent the formation of brittle intermetallic compounds such as ZrW 2 . Traditional polishing techniques prove inadequate because each constituent metal requires a different polishing approach based on its unique material properties. The methodology outlined includes a sequential process involving conductive epoxy mounting, successive grinding and polishing with specific abrasives, and a final chemical-mechanical polish using a colloidal silica-based solution. Optical microscopy confirmed that this multi-step process successfully produced scratch-free surfaces and minimized surface relief across the different metal interfaces. Although developed for refractory metals, this approach shows promise for other layered structures comprised of transition metals, offering a meticulous yet effective technique for high-quality metallographic sample preparation.

Newberry, Daniel [Oak Ridge National Laboratory (O↗

ZnO Films on {001}-Cut <110>-Propagating GaAs Substrates for Surface Acoustic Wave Device Applications

A potential application for piezoelectric films on GaAs substrates is the monolithic integration of surface acoustic wave (SAW) devices with GaAs electronics. Knowledge of the SAW properties of the layered structure is critical for the optimum and accurate design of such devices. The acoustic properties of ZnO films sputtered on {001}-cut <110> -propagating GaAs substrates are investigated in this article, including SAW Velocity effective piezoelectric coupling constant, propagation loss. diffraction, velocity surface, and reflectivity of shorted and open metallic gratings. The measurements of these essential SAW properties for the frequency range between 180 and 360 MHz have been performed using a knife-edge laser probe for film thicknesses over the range of 1.6-4 micron and with films or different grain sizes. The high quality of dc triode sputtered films was observed as evidenced by high K(exp 2) and low attenuation. The measurements of the velocity surface, which directly affects the SAW diffraction, on the bare and metalized ZnO on SiO2, or Si3N4 on {001}-cut GaAs samples are reported using two different techniques: 1) knife-edge laser probe, 2) line-focus-beam scanning acoustic microscope. It was found that near the <110> propagation direction, the focusing SAW property of the bare GaAs changes into a nonfocusing one for the layered structure, but a reversed phenomenon exists near the <100> direction. Furthermore, to some extent the diffraction of the substrate can be controlled with the film thickness. The reflectivity of shorted and open gratings are also analyzed and measured. Zero reflectivity is observed for a shorted grating. There is good agreement between the measured data and theoretical values.

Kim, Yoonkee↗

ZnO films on /001/-cut (110)-propagating GaAs substrates for surface acoustic wave device applications

A potential application for piezoelectric films substrates is the monolithic integration of surface acoustic wave (SAW) devices with GaAs electronics. Knowledge of the SAW properties of the layered structure is critical for the optimum and accurate design of such devices. The acoustic properties of ZnO films sputtered on /001/-cut group of (110) zone axes-propagating GaAs substrates are investigated in this article, including SAW velocity, effective piezoelectric coupling constant, propagation loss, diffraction, velocity surface, and reflectivity of shorted and open metallic gratings. The measurements of these essential SAW properties for the frequency range between 180 and 360 MHz have been performed using a knife-edge laser probe for film thicknesses over the range of 1.6-4 micron and with films of different grain sizes. The high quality of dc triode sputtered films was observed as evidenced by high K(sup 2) and low attenuation. The measurements of the velocity surface, which directly affects the SAW diffraction, on the bare and metalized ZnO on SiO2 or Si3N4 on /001/-cut GaAs samples are reported using two different techniques: (1) knife-edge laser probe, (2) line-focus-beam scanning acoustic microscope. It was found that near the group of (110) zone axes propagation direction, the focusing SAW property of the bare GaAs changes into a nonfocusing one for the layered structure, but a reversed phenomenon exists near the (100) direction. Furthermore, to some extent the diffraction of the substrate can be controlled with the film thickness. The reflectivity of shorted and open gratings are also analyzed and measured. Zero reflectivity is observed for a shorted grating. There is good agreement between the measured data and theoretical values.

Hickernell, Frederick S.↗