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At least 1,783 records · Page 99

Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode

Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.

Lee, Steven↗

Effect of heterostructure engineering on electronic structure and transport properties of two-dimensional halide perovskites

Organic-inorganic halide perovskite solar cells have attracted much attention due to their low-cost fabrication, flexibility, and high-power conversion efficiency. More recent efforts show that the reduction from three- to two-dimensions (2D) of organic–inorganic halide perovskites promises an exciting opportunity to tune their electronic properties. Here, we explore the effect of reduced dimensionality and heterostructure engineering on the intrinsic material properties, such as energy stability, bandgap and transport properties of 2D hybrid organic–inorganic halide perovskites using first-principles density functional theory. We show that the energy stability of engineered perovskite heterostructures is significantly enhanced. The heterostructures with improved stability also show excellent transport properties similar to their bulk counterparts. Furthermore, these layered chemistries demonstrate the advantage of a broad range of tunable bandgaps and high-absorption coefficient in the visible spectrum. The proposed 2D heterostructured material holds potential for nano-optoelectronic devices as well as for effective photovoltaics.

36 MATERIALS SCIENCE↗

Global properties of nuclei at finite-temperature within the covariant energy density functional theory

In stellar environments nuclei appear at finite temperatures, becoming extremely hot in core-collapse supernovae and neutron-star mergers. However, due to theoretical and computational complexity, most model calculations of nuclear properties are performed at zero temperature, while those existing at finite temperatures are limited only to selected regions of the nuclide chart. In this study we perform the global calculation of nuclear properties for even-even 8 ≤ Z ≤ 104 nuclei at temperatures in range 0 ≤ T ≤ 2 MeV. Calculations are based on the finite-temperature relativistic Hartree-Bogoliubov model supplemented by the Bonche-Levit-Vautherin vapor subtraction procedure. We find that near the neutron-drip line the continuum states have significant contribution already at moderate temperature T ≈ 1 MeV, thus emphasizing the necessity of the vapor subtraction procedure. Results include neutron emission lifetimes, quadrupole deformations, neutron-skin thickness, proton and neutron pairing gaps, entropy and excitation energy. Up to the temperature T ≈ 1 MeV, the nuclear landscape is influenced only moderately by the finite-temperature effects, mainly by reducing the pairing correlations. Here, as the temperature increases further, the effects on nuclear structures become pronounced, reducing both the deformations and the shell effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Investigation of Sooting in Microgravity Droplet Combustion: Fuel-Dependent Effects

Kumagai and coworkers first performed microgravity droplet combustion experiments [Kumagai, 1957]. The primary goal of these early experiments were to validate simple 'd(sup 2)-law models [Spalding, 1954, Godsave, 1954] Inherent in the 'd(sup 2) -law' formulation and in the scope of the experimental observation is the neglect of sooting behavior. In fact, the influence of sooting has not received much attention until more recent works [Choi et al., 1990; Jackson et al., 1991; Jackson and Avedisian, 1994; Choi and Lee, 1996; Jackson and Avedisian, 1996; Lee et al., 1998]:. Choi and Lee measured soot volume fraction for microgravity droplet flames using full-field light extinction and subsequent tomographic inversion [Choi and Lee, 1996]. In this investigation, soot concentrations were measured for heptane droplets and it was reported that soot concentrations were considerably higher in microgravity compared to the normal gravity flame. It was reasoned that the absence of buoyancy and the effects of thermophoresis resulted in the higher soot concentrations. Lee et al. [1998] performed soot measurement experiments by varying the initial droplet diameter and found marked influence of sooting on the droplet burning behavior. There is growing sentiment that sooting in droplet combustion must no longer be neglected and that "perhaps one of the most important outstanding contributions of (micro)g droplet combustion is the observation that in the absence of asymmetrical forced and natural convection, a soot shell is formed between the droplet surface and the flame, exerting an influence on the droplet combustion response far greater than previously recognized." [Law and Faeth, 1994]. One of the methods that we are exploring to control the degree of sooting in microgravity is to use different fuels. The effect of fuel structure on sooting propensity has been investigated for over-ventilated concentric coflowing buoyant diffusion flames. (Glassman, 1996]. In these investigations, the fuel flowrate was increased until smoke was observed to escape from the "luminous visible flame" [Glassman, 1996]. A total of 29 fuels were used in order to characterize relative sooting propensity. The sooting propensity of a particular fuel was assessed by comparing the flowrates for soot emission from the tip of the flame. It was reported that the sooting tendency for diffusion flames increased for fuels with higher rates of pyrolysis. Randolph and Law [1986 and not 1994] also examined the effect of fuel structure on droplet sooting behavior. In their experiments the droplets were separated from the bulk gas stream and quenched with nitrogen prior to gravimetric measurements. A variety of fuels were studied, namely aromatics, phenyl-alkanes and alkanes. The results were in qualitative agreement with the work of Glassman [1986]. Vander Wal et al. [1994] performed relative soot concentration measurements using laser-induced incandescence for heptane and decane fuel droplets burning under normal-gravity conditions. It was found that soot volume fractions for decane was more than a factor of two larger than that for heptane. Although the normal-gravity investigations have provided some important insights regarding the influence of fuel structure on the sooting behavior of droplet flames, results cannot be easily extrapolated for microgravity studies since increased residence times and thermophoretic effects must be considered in greater detail. Several studies have compared sooting behavior of different fuel droplets burning under microgravity conditions [Card and Choi, 1990; Jackson et al., 1991; Jackson and Avedisian, 1994], however, detailed quantitative results were not provided. In all of these previous studies, the degree of sooting was only visually assessed from an incandescent backlighted image of the soot containing region. Such techniques can provide misleading results regarding sooting behavior [Choi, 1996].

Manzello, Samuel L.↗

Applied-field magnetic structure and spectroscopy shifts of the effective spin-$\frac{1}{2}$ 𝑋⁢𝑌-like magnet Li 2 ⁢CoCl 4

Insulators containing chains of magnetic transition metal cations provide platforms for probing spin-$\frac{1}{2}$ dynamics and quantum critical behavior. Li 2 ⁢ CoCl 4 contains edge-sharing CoCl 6 octahedra that form chains along the crystallographic 𝑐 axis and orders antiferromagnetically at zero field, but questions remain about its applied-field magnetic structure and the Co 2+ spin state. Here, in this study, we show with neutron diffraction on a polycrystalline sample how the antialigned chains of cobalt moments begin to transition to a ferromagnetic state above 1.6 T. Further, using magnetic resonance absorption measurements and noninteracting spin models, we reveal the strongly anisotropic nature of the Co 2+ ion's 𝑋⁢𝑌-like magnetic behavior (𝑔 ∥ = 2.77 and 𝑔 ⊥ = 5.23) and its 𝐽 = $\frac{1}{2}$ ground state. We therefore supply the magnetic structures and anisotropic description needed to explore the dynamics of the field-driven magnetic phases, laying the foundation for further experimental and theoretical studies.

Riedel, Zachary W. [Univ. of Illinois at Urbana-Ch↗

Effects of gravitational stress, hypokinesia and hypodynamia on the structure of the vascular bed of the spleen

The effects of two extreme factors, hypokinesia and hypodynamia, on spleen vascular beds were studied on 180 male and female albino rats. Vessels were studied by roentgenography, microroentgenography, clearing of sections and histology. Gravity stress yielded construction of all links of arterial bed and of order 5-7 veins. Large intraorganic vein diameters changed significantly but erratically. Hypokinesia in early phases produced pronounced spleen size reduction. Veins and arteries constricted along entire length. Later hypokinetic stages showed arteries still constricted; veins began to dilate from week 4 of hypokinesia. Sinuosity, uneven contours and varicose dilations of walls in large arteries and veins occurred. Abrupt changes in parenchyma, e.g., atrophy of folliculi, narrowing of lumen of central arteries from thickening of muscular wall. After exposure to hypokinesia followed by gravitational stress, pronounced lesions such as deformation of vascular wall, including rupture, in all vessels of the spleen vascular bed.

Nesterenko, N. T.↗

Computation of Large-Scale Structure Jet Noise Sources With Weak Nonlinear Effects Using Linear Euler

An approximate technique is presented for the prediction of the large-scale turbulent structure sound source in a supersonic jet. A linearized Euler equations code is used to solve for the flow disturbances within and near a jet with a given mean flow. Assuming a normal mode composition for the wave-like disturbances, the linear radial profiles are used in an integration of the Navier-Stokes equations. This results in a set of ordinary differential equations representing the weakly nonlinear self-interactions of the modes along with their interaction with the mean flow. Solutions are then used to correct the amplitude of the disturbances that represent the source of large-scale turbulent structure sound in the jet.

Dahl, Milo D.↗

Effect of cholesterol on nano-structural alteration of light-activatable liposomes via laser irradiation: Small angle neutron scattering study

Although the light-activated liposomes have been extensively studied for drug delivery applications, the fundamental mechanism of the drug release based on lipid compositions has not been fully understood. Especially, despite the extensive use of cholesterol in the lipid composition, the role of cholesterol in the light-activated drug release has not been studied. Here, in this study, the influence of cholesterol on drug release from light-responsive drug-encapsulated liposomes after activated by near infrared (NIR) laser was investigated. We prepared methotrexate (MTX)-encapsulated DSPC liposomes consisting of 0 mol% (—Chol) or 35 mol% cholesterol (+Chol), with (+Au) or without gold nanorods (—Au) on the lipid bilayer to compare drug release, morphological changes, and nanostructures after laser irradiations. Transmission electron microscopy (TEM) and small angel neutron scattering (SANS) data revealed that only +Chol +Au liposomes showed partial aggregation of the liposomes after laser irradiation. Similar trends on the drug release and structural change were observed when the liposomes were heated to above chain-transition temperature. Overall, we have found that (1) inclusion of 35 mol% cholesterol enhanced the permeability of lipid bilayers above T c ; (2) the mechanism of laser-activated liposomal drug delivery is disrupting lipid bilayer membranes by the photothermal effect in the presence of plasmonic materials. By understanding the fundamentals of the technology, precise controlled drug release at a targeted site with great stability and repeatability is anticipated.

59 BASIC BIOLOGICAL SCIENCES↗

Gene Expression and Structural Skeletal Responses to Long-Duration Simulated Microgravity in Rats

Spaceflight has deleterious effects on skeletal structure and function, specifically causingprofound loss in bone mass, density, and strength, as well as changes in expression levels of genes related to oxidative stress [Hyeon et al., Smith et al.]. It is known that bone resorption remains elevated after spaceflight and that bone density and strength fail to recover completely even years following spaceflight [Smith et al., Carpenter et al.]. However, our current understanding of the signaling pathways and molecular mechanisms that control bone loss and that link oxidative stress, bone resorption, and mechanical unloading of skeletal tissue is incomplete. Here, we aim to examine skeletal responses to simulated long-duration spaceflight on bone loss using the ground-based hindlimb unloading (HU) model in adult (9 months old) male rats. We hypothesized that simulated microgravity leads to the temporal regulation of oxidative-defense genes and pro-osteoclastogenic factors, showing progression and eventual plateau during long-term unloading, and that transient changes at early timepoints in these pathways precede skeletal adaptations to long-duration unloading. We will identify oxidativestress and bone resorption-related changes using global gene expression analysis (Affymetrix arrays) for both acute (within 14 days) and long-term timepoints (90 days). We will also use quantitative PCR to examine changes in expression of genes related to oxidative metabolism (e.g. Nrf2, SOD-1), bone turnover (resorption and formation markers, e.g. TRAP, osteocalcin respectively, SOST), and osteoclastogenesis (e.g. RANKL, OPG) at both early and late timepoints. We will then use detailed microarchitectural and structural analysis through microcomputed tomography to relate gene expression changes with structural changes in bone, expecting that plateaus in gene expression correlate with long-term changes in bone microarchitecture.

Rael, Victoria E.↗

Effects of CELF Pretreatment Severity on Lignin Structure and the Lignin-Based Polyurethane Properties

Conversion of technical lignin into performance biopolymers such as polyurethane offers environmental and economic advantages when combined with production of biofuels from biomass sugars, presenting significant interest toward studying the role of pretreatment on lignin structure and functionality. Co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment, employing acidic aqueous tetrahydrofuran (THF) mixtures, was developed to effectively break down the lignin-carbohydrate matrix and promote extraction of lignin from lignocellulosic biomass with desirable purity and yield. In this study, we report the effects of CELF pretreatment reaction severity on the molecular structure of CELF-extracted lignin and its impact toward the mechanical properties of the resulting lignin-based polyurethanes. Reaction temperature was found to play the most significant role, compared to reaction time and acidity, in manipulating structural features such as molecular weight, functionality and intra-polymer structure. At the severe reaction conditions at 180°C, the order of reactivity for primary lignin interlinkages characterized by semiquantitative HSQC NMR analysis were found to be β-ether > phenylcoumaran (β−5′) > resinol (β−β′) facilitating a high degree of depolymerization and yielding a high frequency of free phenolics and reduced aliphatic hydroxyl groups. All side-chain interlinkages were depleted converting guaiacyl subunits into condensed forms, while still retaining uncondensed syringyl subunits. Under the mild 150°C temperature reaction, CELF lignin had higher molecular weight and retained more β-ether interlinkages. The results from CELF lignin-based polyurethane synthesis indicated that the tensile properties depended on the miscibility of CELF lignin with other components and low molecular weight cuts improved the dispersion of lignin in the polyurethane network. Pre-mixing of CELF with poly(ethylene glycol) (PEG) reduced the brittleness and improved the ductility of the CELF lignin-PEG polyurethanes.

59 BASIC BIOLOGICAL SCIENCES↗

Surface chemistry and composition-induced variation of laser interference-based surface treatment of Al alloys

A key limitation for the use of aluminum alloys in multi-material structural components is effective surface cleaning and texturing techniques to improve the quality of structural joints. In this study, the surface and sub-surface chemistries are investigated for a novel surface treatment method using laser interferometry produced by two beams of a pulsed Nd:YAG laser. Surfaces of AA 5128 aluminum alloy were treated using a two-beam laser interference setup, enabling the structuring of the surface at length scales much less than that of the laser beam. Periodic and patterned surface structures were created by the interference power profile through ablation of deposits and debris and melting and re-solidification of the near-surface region during laser-treatment. Chemical changes to the Al alloy surface induced by laser treatment were examined in detail in this study using both x-ray photoelectron spectroscopy (XPS) and scanning Auger microanalysis (SAM) as a function of number of interfering laser shots. XPS surface analysis indicates that this laser technique is effective at cleaning aluminum surfaces. Furthermore, SAM data indicated that there is a compositional-induced variation of Mg due to laser-interference as Mg-rich areas were found in periodic interference-structured ridges.

36 MATERIALS SCIENCE↗

Heterogenized Molecular Catalysts: Vibrational Sum-Frequency Spectroscopic, Electrochemical, and Theoretical Investigations

Rhenium and manganese bipyridyl tricarbonyl complexes have attracted intense interest for their promising applications in photocatalytic and electrocatalytic CO 2 reduction in both homogeneous and heterogenized systems. To date, there have been extensive studies on immobilizing Re catalysts on solid surfaces for higher catalytic efficiency, reduced catalyst loading, and convenient product separation. However, in order for the heterogenized molecular catalysts to achieve the combination of the best aspects of homogeneous and heterogeneous catalysts, it is essential to understand the fundamental physicochemical properties of such heterogeneous systems, such as surface-bound structures of Re/Mn catalysts, substrate–adsorbate interactions, and photoinduced or electric-field-induced effects on Re/Mn catalysts. For example, the surface may act to (un)block substrates, (un)trap charges, (de)stabilize particular intermediates (and thus affect scaling relations), and shift potentials in different directions, just as protein environments do. The close collaboration between the Lian, Batista, and Kubiak groups has resulted in an integrated approach to investigate how the semiconductor or metal surface affects the properties of the attached catalyst. Synthetic strategies to achieve stable and controlled attachment of Re/Mn molecular catalysts have been developed. Steady-state, time-resolved, and electrochemical vibrational sum-frequency generation (SFG) spectroscopic studies have provided insight into the effects of interfacial structures, ultrafast vibrational energy relaxation, and electric field on the Re/Mn catalysts, respectively. Various computational methods utilizing density functional theory (DFT) have been developed and applied to determine the molecular orientation by direct comparison to spectroscopy, unravel vibrational energy relaxation mechanisms, and quantify the interfacial electric field strength of the Re/Mn catalyst systems. This Account starts with a discussion of the recent progress in determining the surface-bound structures of Re catalysts on semiconductor and Au surfaces by a combined vibrational SFG and DFT study. The effects of crystal facet, length of anchoring ligands, and doping of the semiconductor on the bound structures of Re catalysts and of the substrate itself are discussed. This is followed by a summary of the progress in understanding the vibrational relaxation (VR) dynamics of Re catalysts covalently adsorbed on semiconductor and metal surfaces. The VR processes of Re catalysts on TiO 2 films and TiO 2 single crystals and a Re catalyst tethered on Au, particularly the role of electron–hole pair (EHP)-induced coupling on the VR of the Re catalyst bound on Au, are discussed. The Account also summarizes recent studies in quantifying the electric field strength experienced by the catalytically active site of the Re/Mn catalyst bound on a Au electrode based on a combined electrochemical SFG and DFT study of the Stark tuning of the CO stretching modes of these catalysts. Finally, future research directions on surface-immobilized molecular catalyst systems are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Case Study on the Application of a Structured Experimental Method for Optimal Parameter Design of a Complex Control System

This report documents a case study on the application of Reliability Engineering techniques to achieve an optimal balance between performance and robustness by tuning the functional parameters of a complex non-linear control system. For complex systems with intricate and non-linear patterns of interaction between system components, analytical derivation of a mathematical model of system performance and robustness in terms of functional parameters may not be feasible or cost-effective. The demonstrated approach is simple, structured, effective, repeatable, and cost and time efficient. This general approach is suitable for a wide range of systems.

Torres-Pomales, Wilfredo↗

Optimization of flexible wing structures subject to strength and induced drag constraints

An optimization procedure for designing wing structures subject to stress, strain, and drag constraints is presented. The optimization method utilizes an extended penalty function formulation for converting the constrained problem into a series of unconstrained ones. Newton's method is used to solve the unconstrained problems. An iterative analysis procedure is used to obtain the displacements of the wing structure including the effects of load redistribution due to the flexibility of the structure. The induced drag is calculated from the lift distribution. Approximate expressions for the constraints used during major portions of the optimization process enhance the efficiency of the procedure. A typical fighter wing is used to demonstrate the procedure. Aluminum and composite material designs are obtained. The tradeoff between weight savings and drag reduction is investigated.

Haftka, R. T.↗

Stabilizing Anionic Redox Chemistry in a Mn-Based Layered Oxide Cathode Constructed by Li-Deficient Pristine State

Li-rich cathode materials are of significant interest for coupling anionic redox with cationic redox chemistry to achieve high-energy-density batteries. However, lattice oxygen loss and derived structure distortion would induce serious capacity loss and voltage decay, further hindering its practical application. Herein, a novel Li-rich cathode material, O3-type Li 0.6 [Li 0.2 Mn 0.8 ]O 2 , is developed with the pristine state displaying both a Li excess in the transition metal layer and a deficiency in the alkali metal layer. Benefiting from stable structure evolution and Li migration processes, not only can high reversible capacity (≈329 mAh g -1 ) be harvested but also irreversible/reversible anionic/cationic redox reactions are comprehensively assigned via the combination of in/ex situ spectroscopies. Furthermore, irreversible lattice oxygen loss and structure distortion are effectively restrained, resulting in long-term cycle stability (capacity drop of 0.045% per cycle, 500 cycles). Altogether, tuning the Li state in the alkali metal layer presents a promising way for modification of high-capacity Li-rich cathode candidates.

anionic redox reactions↗

Peeling back the layers: Investigating the effects of polyelectrolyte layering on surface structure and stability of oil-in-water nanoemulsions

Layer-by-layer deposition of polyelectrolytes is a useful technique for modifying surface functionalities. For drug delivery systems, alternating layers of biopolymers coat nanoemulsions, which house and protect the cargo until the time and destination of delivery. In this report we investigate molecular factors contributing to the stability and interfacial properties of nanoemulsions prepared by a co-adsorption of polymers poly(styrene sulfonate) and polyethylenimine (PEI), and surfactant dodecyltrimethylammonium bromide. We hypothesize the interplay between electrosteric and hydrophobic effects upon multi-polymer co-adsorption contributes to both macroscopic and molecular-level interfacial properties of nanoemulsions. To probe interfacial layering properties, we use vibrational sum frequency scattering spectroscopy with ζ -potential measurements to determine the adsorptive behavior and molecular conformational arrangement of the polymer layers. Complementing these interfacial studies are dynamic light scattering experiments measuring the nanoemulsion size distribution and polydispersity index over a 30-day period. Our light scattering, ζ -potential, and spectroscopic results of the nanoemulsion surface show that the duration of droplet stability and the degree of molecular orientation of adsorbed polymers can be tuned by surfactant concentration, PEI concentration, and pH. These results illustrate how molecular surface properties of multi-polymer coated nanoemulsions contribute to synergistic effects and droplet stability, enabling advancements in applications surrounding biopharmaceuticals, cosmetics, and food sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗