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At least 37 records · Page 2

Asymmetric Dianhyrdrides and Methods of Making the Same

A method for preparing asymmetric 3,4'-(hexafluroisopropylidene) dipthalic anhydride (a-6FDA) and asymmetric 3,4'-(methylene)diphthalic anhydride (a-MDPA) from asymmetric 2,3,3',4'-benzophenone dianhydride (a-BTDA). First, a-BTDA is converted to its corresponding N-alkyl or N-phenyl bisimides by reacting with either methylamine or aniline. The sequential addition of two trifluoromethyl (CF.sub.3) groups to the carbonyl unit of a-BTDA produce the corresponding bisimides of asymmetric 6FDA, which is hydrolyzed to the asymmetric 6F-tetracarboxylic acid followed by cyclodehydration to obtain asymmetric 6F-dianhydride (a-6FDA). Separately, the carbonyl unit of bisimides of a-BTDA is reduced to a methylene unit to afford the corresponding bisimides of asymmetric 3,4'-(methylene)diphthalic anhydride, which is hydrolyzed to the asymmetric methylene tetracarboxylic acid followed by cyclodehydration to obtain 3,4'-(methylene)diphthalic anhydride (a-MDPA).

Chuang, Chun-Hua↗

On the role of asymmetric molecular geometry in high-performance organic solar cells

Although asymmetric molecular design has been widely demonstrated effective for organic photovoltaics (OPVs), the correlation between asymmetric molecular geometry and their optoelectronic properties is still unclear. To access this issue, we have designed and synthesized several symmetric-asymmetric non-fullerene acceptors (NFAs) pairs with identical physical and optoelectronic properties. Interestingly, we found that the asymmetric NFAs universally exhibited increased open-circuit voltage compared to their symmetric counterparts, due to the reduced non-radiative charge recombination. From our molecular-dynamic simulations, the asymmetric NFA naturally exhibits more diverse molecular interaction patterns at the donor (D):acceptor (A) interface as compared to the symmetric ones, as well as higher D:A interfacial charge-transfer state energy. Moreover, it is observed that the asymmetric structure can effectively suppress triplet state formation. These advantages enable a best efficiency of 18.80%, which is one of the champion results among binary OPVs. Therefore, this work unambiguously demonstrates the unique advantage of asymmetric molecular geometry, unveils the underlying mechanism, and highlights the manipulation of D:A interface as an important consideration for future molecular design.

14 SOLAR ENERGY↗

Asymmetric Bulkheads for Cylindrical Pressure Vessels

Asymmetric bulkheads are proposed for the ends of vertically oriented cylindrical pressure vessels. These bulkheads, which would feature both convex and concave contours, would offer advantages over purely convex, purely concave, and flat bulkheads (see figure). Intended originally to be applied to large tanks that hold propellant liquids for launching spacecraft, the asymmetric-bulkhead concept may also be attractive for terrestrial pressure vessels for which there are requirements to maximize volumetric and mass efficiencies. A description of the relative advantages and disadvantages of prior symmetric bulkhead configurations is prerequisite to understanding the advantages of the proposed asymmetric configuration: In order to obtain adequate strength, flat bulkheads must be made thicker, relative to concave and convex bulkheads; the difference in thickness is such that, other things being equal, pressure vessels with flat bulkheads must be made heavier than ones with concave or convex bulkheads. Convex bulkhead designs increase overall tank lengths, thereby necessitating additional supporting structure for keeping tanks vertical. Concave bulkhead configurations increase tank lengths and detract from volumetric efficiency, even though they do not necessitate additional supporting structure. The shape of a bulkhead affects the proportion of residual fluid in a tank that is, the portion of fluid that unavoidably remains in the tank during outflow and hence cannot be used. In this regard, a flat bulkhead is disadvantageous in two respects: (1) It lacks a single low point for optimum placement of an outlet and (2) a vortex that forms at the outlet during outflow prevents a relatively large amount of fluid from leaving the tank. A concave bulkhead also lacks a single low point for optimum placement of an outlet. Like purely concave and purely convex bulkhead configurations, the proposed asymmetric bulkhead configurations would be more mass-efficient than is the flat bulkhead configuration. In comparison with both purely convex and purely concave configurations, the proposed asymmetric configurations would offer greater volumetric efficiency. Relative to a purely convex bulkhead configuration, the corresponding asymmetric configuration would result in a shorter tank, thus demanding less supporting structure. An asymmetric configuration provides a low point for optimum location of a drain, and the convex shape at the drain location minimizes the amount of residual fluid.

Ford, Donald B.↗

Oxides and Nitrides with Asymmetric Pore Structure from Block Copolymer Co–Assembly and Non–Solvent Induced Phase Separation

Materials combining an asymmetric pore structure with mesopores everywhere enable high surface area accessibility and fast transport, making them attractive for e.g., energy conversion and storage applications. Block copolymer (BCP)/inorganic precursor co-assembly combined with non-solvent induced phase separation (NIPS) provides a route to materials in which a mesoporous top surface layer merges into an asymmetric support with graded porosity along the film normal and mesopores throughout. Here, the co-assembly and non-solvent-induced phase separation (CNIPS) of poly(isoprene)-b-poly(styrene)-b-poly(4-vinylpyridine) (ISV) triblock terpolymer and titanium dioxide (TiO 2 ) sol-gel nanoparticlesare reported. Heat-treatment in air results in free-standing asymmetric porous TiO 2 . Further thermal processing in ammonia results in free-standing asymmetric porous titanium nitride (TiN). processing changes alter structural membrane characteristics is demonstrated. Changing the CNIPS evaporation time results in various membrane cross-sections ( finger-like to sponge-like). Further, oxide and nitride material composition, crystallinity, and porosity are tuned by varying thermal processing conditions. Finally, thermal processing condition effects are probed on phase-pure asymmetric nitride membrane behavior using cyclic voltammetry to elucidate their influence, e.g., on specific capacitance. Results provide further insights into improving asymmetric and porous materials for applications including energy conversion and storage, separation, and catalysis and motivate a further expansion of CNIPS to other (in)organic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Superhydrophobic composite asymmetric electrospun membrane for sustainable vacuum assisted air gap membrane distillation

Membrane distillation (MD) relies on superhydrophobic membranes that must achieve the competing goals of high liquid entry pressure (LEP) and high permeability. Here, in this study, we developed the first superhydrophobic composite electrospun asymmetric membrane using fluorinated graphite (FG). We also provided among the first comparisons of the relative benefits of membrane asymmetry and composite coatings via 3D electrospinning and spraying. FG particles increased the roughness and reduced the zeta potential of the membranes. Superhydrophobic composite membranes had a contact angle of 157° (sliding angle of 7°) and an LEP of 327 kPa. Long-term MD testing revealed that FG particles could increase MD's sustainability while decreasing membrane wetting. Vacuum-assisted air gap membrane distillation (V-AGMD) showed that the composite asymmetric membrane outperformed the non-asymmetric version (composite nanofiber) membrane by 21 % in average water flux and 25 % in average thermal efficiency because of the asymmetric structure of the membrane. The numerical model developed for the V-AGMD system also successfully predicted the water flux generated experimentally from the composite nanofiber and composite asymmetric membranes. Our results confirmed that electrospun asymmetric FG membranes with high contact angle, low sliding angle, high permeability, and high gained output ratio (GOR) would be promising candidates for sustainable MD.

36 MATERIALS SCIENCE↗

Direct Phase-Angle Detection for Three-Phase Inverters in Asymmetrical Power Grids

This paper introduces a signal reformation based direct phase-angle detection (DPD-SR) technique for three-phase inverters supporting asymmetrical grids. Asymmetries in three-phase systems may happen because of unbalanced three-phase loads, which can lead to the voltage asymmetry at the terminals of grid-tied inverters. The proposed DPD-SR technique can detect the voltage phase-angle under asymmetrical conditions. The DPD-SR technique also offers precise and rapid phase-angle detection via signal reformation and trigonometric functions. In essence, the phase-angle detection is directly derived from the trigonometric properties of the line-line voltages, while signal reformation is implemented to handle asymmetrical voltages. The proposed method measures two line-line voltages and detects the phase-angle of a three-phase system under both symmetrical and asymmetrical conditions. Unlike classical phase-locked loop (PLL) techniques, DPD-SR does not need any closed-loop PI controller, which significantly reduces the complexity and the delay in detecting the phase-angle. In this paper, the efficacy of the proposed technique is examined in comparison with the state-of-the-art PLLs under asymmetrical conditions via a set of laboratory experiments. Here, the performance of the phase-angle detection is also tested as part of an inverter feeding an asymmetrical grid.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Microscopic origin of reflection-asymmetric nuclear shapes

The presence of nuclear ground states with stable reflection-asymmetric shapes is supported by rich experimental evidence. Theoretical surveys of odd-multipolarity deformations predict the existence of pear-shaped isotopes in several fairly localized regions of the nuclear landscape in the vicinity of near-lying single-particle shells with Δℓ = Δj = 3. We analyze the role of isoscalar, isovector, neutron-proton, neutron-neutron, and proton-proton multipole interaction energies in inducing the onset of reflection-asymmetric ground-state deformations. The calculations are performed in the framework of axial reflection-asymmetric Hartree-Fock-Bogoliubov theory using two Skyrme energy-density functionals and density-dependent pairing force. We show that reflection-asymmetric ground-state shapes of atomic nuclei are driven by the odd-multipolarity neutron-proton (or isoscalar) part of the nuclear interaction energy. This result is consistent with the particle-vibration picture, in which the main driver of octupole instability is the isoscalar octupole-octupole interaction giving rise to large E3 polarizability. The necessary condition for the appearance of localized regions of pear-shaped nuclei in the nuclear landscape is the presence of parity doublets involving Δℓ = Δj = 3 proton or neutron single-particle shells. This condition alone is, however, not sufficient to determine whether pear shapes actually appear, and, if so, what the corresponding reflection-asymmetric deformation energies are. The predicted small reflection-asymmetric deformation energies result from dramatic cancellations between even- and odd-multipolarity components of the nuclear binding energy.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Asymmetric lateral-directional characteristics of pointed bodies of revolution at high angles of attack

A low-speed wind-tunnel investigation was conducted in order to determine the cause of asymmetric yawing moments produced by long pointed fuselage nose shapes at high angles of attack. Force tests were conducted with a cone, tangent-ogive model, and a paraboloid of revolution over a range of Reynolds numbers from 0.15 million to 0.35 million for an angle-of-attack range from 0 deg to 75 deg and an angle-of-sideslip range of plus or minus 30 deg. Tuft and smoke flow-visualization tests were also conducted to aid in the analysis. Large asymmetric yawing moments were obtained for the cone and tangent-ogive body at high angles of attack (of the order of 40 to 60 deg). These large moments were caused by asymmetric shedding of vortex sheets off the long pointed nose. The asymmetric moments could be eliminated by use of symmetrically arranged strikes on the nose. The paraboloid of revolution did not produce a strong asymmetric flow field at high angles of attack and did not exhibit asymmetric moments.

Coe, P. L., Jr.↗

Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides

This invention relates to processes for preparing asymmetrical biphenyl tetracarboxylic acids and the corresponding asymmetrical dianhydrides, namely 2,3,3',4'-biphenyl dianhydride (a-BPDA), 2,3,3',4'-benzophenone dianhydride (a-BTDA) and 3,4'-methylenediphthalic anhydride (-MDPA). By cross-coupling reactions of reactive metal substituted o-xylenes or by cross-coupling o-xylene derivatives in the presence of catalysts, this invention specifically produces asymmetrical biphenyl intermediates that are subsequently oxidized or hydrolyzed and oxidized to provide asymmetric biphenyl tetracarboxylic acids in comparatively high yields. These asymmetrical biphenyl tetracarboxylic acids are subsequently converted to the corresponding asymmetrical dianhydrides without contamination by symmetrical biphenyl dianhydrides.

Chuang, Chun-Hua↗

Finite Element Contact Analysis and Redesign of Rotorcraft Planetary Gear Sets With Asymmetric Profiles

This article explores the use of asymmetric gear teeth for rotorcraft main rotor planetary gearsets. Two baseline designs having symmetric gear teeth were selected for redesign studies. Finite element-based contact analyses were used to compare designs. Bending stress predictions for the two existing baseline designs were compared to strain gage measurements to confirm the suitability of the modeling. The same modeling method is then used to assess design changes to improve the bending stress and contact pressure magnitudes using asymmetric tooth profiles. For the first redesign study, the selected gearset is mildly asymmetric, with a 4° difference in pressure angles between the two sides of a tooth. For the second redesign study, the selected gearset is strongly asymmetric with a 18° difference in pressure angles. The results demonstrate that the asymmetric tooth approach provides additional design flexibility toward balancing the contact stresses and bending stresses of the sun, planet, and ring members.

gear↗

Design of Diverse Asymmetric Pockets in De Novo Homo-oligomeric Proteins

A challenge for design of protein–small-molecule recognition is that incorporation of cavities with size, shape, and composition suitable for specific recognition can considerably destabilize protein monomers. This challenge can be overcome through binding pockets formed at homo-oligomeric interfaces between folded monomers. Interfaces surrounding the central homo-oligomer symmetry axes necessarily have the same symmetry and so may not be well suited to binding asymmetric molecules. To enable general recognition of arbitrary asymmetric substrates and small molecules, we developed an approach to designing asymmetric interfaces at off-axis sites on homo-oligomers, analogous to those found in native homo-oligomeric proteins such as glutamine synthetase. We symmetrically dock curved helical repeat proteins such that they form pockets at the asymmetric interface of the oligomer with sizes ranging from several angstroms, appropriate for binding a single ion, to up to more than 20 Å across. Of the 133 proteins tested, 84 had soluble expression in E. coli, 47 had correct oligomeric states in solution, 35 had small-angle X-ray scattering (SAXS) data largely consistent with design models, and 8 had negative-stain electron microscopy (nsEM) 2D class averages showing the structures coming together as designed. Both an X-ray crystal structure and a cryogenic electron microscopy (cryoEM) structure are close to the computational design models. The nature of these proteins as homo-oligomers allows them to be readily built into higher-order structures such as nanocages, and the asymmetric pockets of these structures open rich possibilities for small-molecule binder design free from the constraints associated with monomer destabilization.

59 BASIC BIOLOGICAL SCIENCES↗

Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. Here we present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

36 MATERIALS SCIENCE↗

Numerical simulation of steady and unsteady asymmetric vortical flow

The unsteady, compressible, thin-layer, Navier-Stokes (NS) equations are solved to simulate steady and unsteady, asymmetric, vortical laminar flow around cones at high incidences and supersonic Mach numbers. The equations are solved by using an implicit, upwind, flux-difference splitting (FDS), finite-volume scheme. The locally conical flow assumption is used and the solutions are obtained by forcing the conserved components of the flowfield vector to be equal at two axial stations located at 0.95 and 1.0. Computational examples cover steady and unsteady asymmetric flows around a circular cone and its control using side strakes. The unsteady asymmetric flow solution around the circular cone has also been validated using the upwind, flux-vector splitting (FVS) scheme with the thin-layer NS equations and the upwind FDS with the full NS equations. The results are in excellent agreement with each other. Unsteady asymmetric flows are also presented for elliptic- and diamond-section cones, which model asymmetric vortex shedding around round- and sharp-edged delta winds.

Kandil, Osama A.↗

Geometric Perturbations and Asymmetric Vortex Shedding about Slender Pointed Bodies

The flow about slender, pointed bodies can be characterized by different states with angle of attack. At moderate-to-high angles of attack (alpha approx. = 40 deg.), a steady, asymmetric vortex pattern develops along the body, leading to a net lateral force. At higher angles of attack (alpha approx. = 60 deg.), the aft-end of the body develops an unsteady von Karman shedding. As the angle of attack approaches 90 deg., the entire body length exhibits a time-dependent vortex shedding pattern. The current work uses three-dimensional, thin-layer Navier-Stokes simulations to investigate the physical mechanisms of asymmetric vortex shedding at alpha = 40 deg. and alpha = 60 deg. The development of an asymmetric vortex pattern via a convective instability mechanism is investigated using tip bumps, surface roughness, and tip curvature. It's found that surface roughness simulations can incite an asymmetric vortex state at alpha = 60 deg. which is consistent with the application of a tip bump, and the experimentally observed flowfield. The unsteady von Karman vortex shedding on the aft. portion of the body is also well resolved. The use of surface roughness did not incite a flow asymmetry at alpha = 40 deg., and it was necessary to simulate tip curvature at this angle of attack in order to generate an asymmetric vortex state.

Murman, Scott M.↗

Geometric Perturbations and Asymmetric vortex shedding About Slender Pointed Bodies

The flow about slender, pointed bodies can be characterized by different states with angle of attack. At moderate-to-high angles of attack (alpha approximately equals 40deg), a steady, asymmetric vortex pattern develops along the body, leading to a net lateral force. At higher angles of attack (alpha approximately equals 60deg), the aft-end of the body develops an unsteady von Karman shedding. As the angle of attack approaches 90deg, the entire body length exhibits a time-dependent vortex shedding pattern. The current work uses three-dimensional, thin-layer Navier-Stokes simulations to investigate the physical mechanisms of asymmetric vortex shedding at alpha = 40deg and alpha = 60deg. The development of an asymmetric vortex pattern via a convective instability mechanism is investigated using tip bumps, surface roughness, and tip curvature. It's found that surface roughness simulations can incite an asymmetric vortex state at alpha = 60deg which is consistent with the application of a tip bumps, and the experimentally observed flowfield. The unsteady von Karman vortex shedding on the aft portion of the body is also well resolved. The use of surface roughness did not incite a flow asymmetry at alpha = 40deg, and it was necessary to simulate tip curvature at this angle of attack in order to generate an asymmetric vortex state.

Murman, Scott M.↗

The Impacts of Dry Dynamic Cores on Asymmetric Hurricane Intensification

The fundamental pathways for tropical cyclone (TC) intensification are explored by considering axisymmetric and asymmetric impulsive thermal perturbations to balanced, TC-like vortices using the dynamic cores of three different nonlinear numerical models. Attempts at reproducing the results of previous work, which used the community WRF Model, revealed a discrepancy with the impacts of purely asymmetric thermal forcing. The current study finds that thermal asymmetries can have an important, largely positive role on the vortex intensification, whereas other studies find that asymmetric impacts are negligible. Analysis of the spectral energetics of each numerical model indicates that the vortex response to asymmetric thermal perturbations is significantly damped in WRF relative to the other models. Spectral kinetic energy budgets show that this anomalous damping is primarily due to the increased removal of kinetic energy from the vertical divergence of the vertical pressure flux, which is related to the flux of inertia-gravity wave energy. The increased kinetic energy in the other two models is shown to originate around the scales of the heating and propagate upscale with time from nonlinear effects. For very large thermal amplitudes (50 K), the anomalous removal of kinetic energy due to inertia-gravity wave activity is much smaller, resulting in good agreement between models. The results of this paper indicate that the numerical treatment of small-scale processes that project strongly onto inertia-gravity wave energy can lead to significant differences in asymmetric TC intensification. Sensitivity tests with different time integration schemes suggest that diffusion entering into the implicit solution procedure is partly responsible for the anomalous damping of energy.

Guimond, Stephen R.↗

Tuning the Mechanical and Electric Properties of Conjugated Polymer Semiconductors: Side–Chain Design Based on Asymmetric Benzodithiophene Building Blocks

Understanding molecular design rules for stretchable polymer semiconductors is important for enabling next generation stretchable electronic circuits. To simultaneously improve both electrical properties and mechanical stretchability, a design strategy is reported in introducing conjugated rigid fused-rings with bulky side groups in semiconducting polymers. In this work, the understanding of this design concept is improved by systematically investigating the effect of different types of bulky side groups asymmetrically substituted on conjugated polymer semiconductor backbones. Specifically, four types of side groups are investigated, including naphthalene (NaPh), biphenyl (PhPh), thienylphenyl (ThPh), and alkylphenyl (C4Ph), asymmetrically substituted on benzodithiophene units, namely asy-BDT. With the four types of side groups installed on BDT-containing conjugated polymers in an asymmetrical fashion, it is observed that they reduced the polymer chain aggregation and film crystallinity, hence improving the film stretchability. Furthermore, the fully conjugated polymer back-bone allows maintenance of good charge carrier mobilities. Specifically, polymer PDPP-C4Ph (with C4Ph side groups) shows the highest mobility in the fully stretchable transistor and maintained its mobility even after being subjected to hundreds of stretching-releasing cycles at 25% strain. Altogether, the results provide anunderstanding of the use of asymmetrically substituted fused-ring conjugated polymer structures to tune mechanical and charge transport properties.

36 MATERIALS SCIENCE↗

Unidirectional Sidechain Engineering to Construct Dual‐Asymmetric Acceptors for 19.23 % Efficiency Organic Solar Cells with Low Energy Loss and Efficient Charge Transfer

Abstract Achieving both high open‐circuit voltage ( V oc ) and short‐circuit current density ( J sc ) to boost power‐conversion efficiency (PCE) is a major challenge for organic solar cells (OSCs), wherein high energy loss ( E loss ) and inefficient charge transfer usually take place. Here, three new Y‐series acceptors of mono‐asymmetric asy‐YC11 and dual‐asymmetric bi‐asy‐YC9 and bi‐asy‐YC12 are developed. They share the same asymmetric D 1 AD 2 (D 1 =thieno[3,2‐ b ]thiophene and D 2 =selenopheno[3,2‐ b ]thiophene) fused‐core but have different unidirectional sidechain on D 1 side, allowing fine‐tuned molecular properties, such as intermolecular interaction, packing pattern, and crystallinity. Among the binary blends, the PM6 : bi‐asy‐YC12 one has better morphology with appropriate phase separation and higher order packing than the PM6 : asy‐YC9 and PM6 : bi‐asy‐YC11 ones. Therefore, the PM6 : bi‐asy‐YC12‐based OSCs offer a higher PCE of 17.16 % with both high V oc and J sc , due to the reduced E loss and efficient charge transfer properties. Inspired by the high V oc and strong NIR‐absorption, bi‐asy‐YC12 is introduced into efficient binary PM6 : L8‐BO to construct ternary OSCs. Thanks to the broadened absorption, optimized morphology, and furtherly minimized E loss , the PM6 : L8‐BO : bi‐asy‐YC12‐based OSCs achieve a champion PCE of 19.23 %, which is one of the highest efficiencies among these annealing‐free devices. Our developed unidirectional sidechain engineering for constructing bi‐asymmetric Y‐series acceptors provides an approach to boost PCE of OSCs.

Chemistry↗