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At least 1,189 records · Page 66

Resilient high-temperature reverse osmosis desalination membranes

Conventional thin-film composite (TFC) reverse osmosis (RO) membranes experience irreversible performance loss at high temperatures, restricting their use in industries with high-temperature streams, including oil and gas, pharmaceuticals, electronics, power generation, food production, and hybrid desalination plants. However, the mechanisms driving the performance decline of TFC membranes at high temperatures remain poorly understood. Herein, we combine controlled experiments, molecular dynamics simulations, and micromechanical modeling to elucidate TFC failure mechanisms and to evaluate thermally resilient thin-film cross-linked (TFX) composite membrane. Upon exposure to elevated temperatures (>60°C), salt rejection of TFC dropped from ~99 to <90%, with irreversible structural damage in the polysulfone layer, confirmed by scanning electron microscopy. In contrast, the TFX membrane maintained ~99% salt rejection and showed no signs of physical degradation up to 80°C. Our combined analyses revealed that TFC membrane failure arises from irreversible pore expansion in the thermoplastic polysulfone support, leading to polyamide film rupture and delamination. TFX membranes resist thermal deformation, enabling ultrahigh-temperature RO desalination and water reuse.

Wu, Jishan [Rice Univ., Houston, TX (United States↗

A high-energy-density lithium-oxygen battery based on a reversible four-electron conversion to lithium oxide

Lithium-oxygen (Li-O 2 ) batteries have attracted much attention owing to the high theoretical energy density afforded by the two-electron reduction of O 2 to lithium peroxide (Li 2 O 2 ). We report an inorganic-electrolyte Li-O 2 cell that cycles at an elevated temperature via highly reversible four-electron redox to form crystalline lithium oxide (Li 2 O). It relies on a bifunctional metal oxide host that catalyzes O–O bond cleavage on discharge, yielding a high capacity of 11 milliampere-hours per square centimeter, and O 2 evolution on charge with very low overpotential. Online mass spectrometry and chemical quantification confirm that oxidation of Li 2 O involves transfer of exactly 4 e – /O 2 . This work shows that Li-O 2 electrochemistry is not intrinsically limited once problems of electrolyte, superoxide, and cathode host are overcome and that coulombic efficiency close to 100% can be achieved.

Xia, C. (ORCID:0000000344062337)↗

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing to the low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP of cyclic acetals using a commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, we synthesize poly(1,3-dioxolane) (PDXL), which demonstrates tensile strength comparable to some commodity polyolefins. Depolymerization of PDXL using strong acid catalysts returns monomer in near-quantitative yield and even proceeds from a commodity plastic waste mixture. Our efficient polymerization method affords a tough thermoplastic that can undergo selective depolymerization to monomer.

Abel, Brooks A.↗

Structural Insights into HIV Reverse Transcriptase Mutations Q151M and Q151M Complex That Confer Multinucleoside Drug Resistance

HIV-1 reverse transcriptase (RT) is targeted by multiple drugs. RT mutations that confer resistance to nucleoside RT inhibitors (NRTIs) emerge during clinical use. Q151M and four associated mutations, A62V, V75I, F77L, and F116Y, were detected in patients failing therapies with dideoxynucleosides (didanosine [ddI], zalcitabine [ddC]) and/or zidovudine (AZT). The cluster of the five mutations is referred to as the Q151M complex (Q151Mc), and an RT or virus containing Q151Mc exhibits resistance to multiple NRTIs. To understand the structural basis for Q151M and Q151Mc resistance, we systematically determined the crystal structures of the wild-type RT/double-stranded DNA (dsDNA)/dATP (complex I), wild-type RT/dsDNA/ddATP (complex II), Q151M RT/dsDNA/dATP (complex III), Q151Mc RT/dsDNA/dATP (complex IV), and Q151Mc RT/dsDNA/ddATP (complex V) ternary complexes. The structures revealed that the deoxyribose rings of dATP and ddATP have 3'-endo and 3'-exo conformations, respectively. The single mutation Q151M introduces conformational perturbation at the deoxynucleoside triphosphate (dNTP)-binding pocket, and the mutated pocket may exist in multiple conformations. The compensatory set of mutations in Q151Mc, particularly F116Y, restricts the side chain flexibility of M151 and helps restore the DNA polymerization efficiency of the enzyme. The altered dNTP-binding pocket in Q151Mc RT has the Q151-R72 hydrogen bond removed and has a switched conformation for the key conserved residue R72 compared to that in wild-type RT. On the basis of a modeled structure of hepatitis B virus (HBV) polymerase, the residues R72, Y116, M151, and M184 in Q151Mc HIV-1 RT are conserved in wild-type HBV polymerase as residues R41, Y89, M171, and M204, respectively; functionally, both Q151Mc HIV-1 and wild-type HBV are resistant to dideoxynucleoside analogs.

59 BASIC BIOLOGICAL SCIENCES↗

Violation of light beam reversibility principle in optical media with a random quasi-zero refractive index

We report on experimental and theoretical evidence of the violation of one of the fundamental principles in the Fresnel optics, namely, light beam reversibility, in new nanostructured composite metamaterials with silver nanoparticle in a polymer matrix. It is shown that optical transmittance of (PMMA + Ag)/glass samples in counter directions is not the same. We propose a theoretical explanation of this phenomenon based on the effect of photon localization on the surface of the composite layer with a random quasizero refractive index.

36 MATERIALS SCIENCE↗

Variety of the Pulsed Magnetization Reversal of an Inhomogeneous Lattice of Anisotropic Nanoparticles

The responses of the magnetic moment of an isolated nanoparticle having a uniaxial anisotropy and the magnetic moment of a planar lattice made of such nanoparticles to a Gaussian magnetic field pulse are studied by computer simulation. The influence of the anisotropy and the field pulse parameters on the precession dynamics is investigated. The periodic dependence of the response time and the final orientation of the magnetic moments on the pulse duration is revealed and analyzed. For a lattice consisting of different types of nanoparticles, the number of final lattice configurations induced by pulsed magnetization reversal is shown to be larger than the number of the types of nanoparticles more than twofold.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of Exchange Interaction Constants on the Magnetization Reversal in a Hard/Soft Magnetic Bilayer Model

A model is developed to study a hard/soft magnetic bilayer in an external magnetic field by the Monte Carlo method. The influence of the constants of the exchange intralayer and interlayer interactions of the hard magnetic and soft magnetic layers on the magnetization reversal in the magnetic bilayer is investigated. The formation of a spin spring is shown to be mainly determined by the exchange interaction in the soft magnetic layer. Phase diagrams are plotted for the magnetic bilayer.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The effect of the electron–phonon interaction on reverse currents of GaAs-based p–n junctions

An algorithm for calculating the parameters of the electron–phonon interaction of the EL2 trap has been developed and implemented based on the example of GaAs. Using the obtained parameters, the field dependences of the probabilities of nonradiative transitions from the trap and reverse currents of the GaAs p–n junctions are calculated, which are in good agreement with the experimental data.

36 MATERIALS SCIENCE↗

Reversible electrochemical modification of the surface of a semiconductor by an atomic-force microscope probe

A technique for reversible surface modification with an atomic-force-microscope (AFM) probe is suggested. In this method, no significant mechanical or topographic changes occur upon a local variation in the surface potential of a sample under the AFM probe. The method allows a controlled relative change in the ohmic resistance of a channel in a Hall bridge within the range 20–25%.

36 MATERIALS SCIENCE↗

Trends in Reverse-Current Change in Tunnel MIS Diodes with Calcium Fluoride on Si(111) Upon the Formation of an Extra Oxide Layer

The currents flowing in metal–CaF{sub 2}–n-Si and metal–SiO{sub 2}–CaF{sub 2}–n-Si structures with the same (about 1.5 nm) fluoride thickness are compared in the reverse-bias mode. It is revealed that the current in the case of a two-layer dielectric can be notably higher within a certain voltage range. Such unexpected behavior is associated with the coexistence of both electron and hole components of the current as well as with the configuration of the SiO{sub 2}–CaF{sub 2} barrier through which tunneling occurs. The results of measurements and explanatory simulation data are presented.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evolution of domain structure and formation of charged domain walls during polarization reversal in lithium niobate single crystals modified by vacuum annealing

The evolution of the domain structure during polarization reversal has been investigated in plates of lithium niobate with spatially inhomogeneous electrical conductivity produced by vacuum annealing. The formation of charged domain walls in the crystal bulk has been studied. Revealed features of the domain growth in the bulk have been attributed to the formation of nanodomains under the pyroelectric field and inhomogeneous spatial distribution of the electric field. Creation of the charged domain walls with controlled parameters is of great interest for domain walls engineering.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetization Reversal of Permalloy Microparticles with the Configuration Anisotropy by Magnetic-Force Microscopy

Abstract—Magnetic force microscopy has been used to study the distribution of the magnetization in permalloy microparticles with a configurational anisotropy. The triangular particles with different degrees of concavity of the lateral sides have been studied. An analysis of the results enables us to state that the particles can be in several quasi-homogeneous stable states. It is shown that the particle magnetization reversal can occur both stepwise and also via an intermediate state in the dependence on the particle orientation. It is demonstrated that the quasi-homogeneous magnetization orientation in a particle can be changed by a magnetic-force microscope probe.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analysis of integrated thyristor switching-off by a reverse gate pulse current

To increase the maximum power current density of an integrated n{sup +}p'Nn'p{sup +}-type thyristor during switching-off by a current pulse in the control circuit, the injection of electrons from the n{sup +} emitter should be interrupted before the recovery of the collector p'N junction. This has been done using a rapidly increasing reverse gate current pulse with an amplitude equal to the amplitude of the power switched-off current. After the interruption of the emitter injection, the remaining current through the device is the current of holes extracted from the collector region via the gate electrode. Like in insulated gate bipolar transistors (IGBTs), the physical mechanism that limits the maximum density of the switch-off current is the dynamic avalanche breakdown, which is initiated by the holes extracted through the space charge region of the collector p'N junctions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Skyrmion dynamics and transverse mobility: skyrmion Hall angle reversal on 2D periodic substrates with dc and biharmonic ac drives

Here we numerically examine the dynamics of a skyrmion interacting with a two-dimensional periodic substrate under dc and biharmonic ac drives. We show that the Magnus force of the skyrmion produces circular orbits that can resonate with the ac drive and the periodicity of the substrate to create quantized motion both parallel and perpendicular to the dc drive. The skyrmion Hall angle exhibits a series of increasing and/or decreasing steps along with strongly fluctuating regimes. In the phase locked regimes, the skyrmion Hall angle is constant and the skyrmion motion consists of periodic orbits encircling an integer number of obstacles per every or every other ac drive cycle. We also observe phases in which the skyrmion moves at 90° with respect to the driving direction even in the presence of damping, a phenomenon called absolute transverse mobility that can exhibit reentrance as a function of dc drive. When the biharmonic ac drives have different amplitudes in the two directions, we find regimes in which the skyrmion Hall angle shows a sign reversal from positive to negative, as well as a reentrant pinning effect in which the skyrmion is mobile at low drives but becomes pinned at higher drives. These behaviors arise due to the combination of the Magnus force with the periodic motion of the skyrmions, which produce Shapiro steps, directional locking, and ratchet effects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantitative Analysis of Color Differences within High Contrast, Low Power Reversible Electrophoretic Displays

Here, quantitative color analysis is performed on videos of high contrast, low power reversible electrophoretic deposition (EPD)-based displays operated under different applied voltages. This analysis is coded in an open-source software, relies on a color differentiation metric, ΔE * 00 , derived from digital video, and provides an intuitive relationship between the operating conditions of the devices and their performance. Time-dependent ΔE * 00 color analysis reveals color relaxation behavior, recoverability for different voltage sequences, and operating conditions that can lead to optimal performance.

36 MATERIALS SCIENCE↗

Highly Reversible Plating/Stripping of Porous Zinc Anodes for Multivalent Zinc Batteries

Zinc continues to garner immense interest due to its versatility as an anode material in several configurations utilizing either alkaline or mild-pH electrolytes. Current research on using mild-pH electrolytes has improved the rechargeability aspect of Zn-based batteries since Zn2+ is solely utilized for plating/stripping of Zn. Several studies have incorporated Zn metal foils, yet, dramatic improvements can be achieved by expressing Zn as a porous structure. Herein, we use a quasi-pulsed electrodeposition process to prepare a conformal Zn coating onto 3D porous copper foam. By tuning the electrodeposition parameters, we achieved an optimal Zn coating that undergoes reversible plating/stripping when tested in symmetric Zn cells, which supported a low overpotential of ~60 mV for up to 100 cycles. We further investigated changes in the surface morphology by studying the Zn surface of both foil and 3D structure using scanning electron microscopy and X-ray micro-computed tomography. Both techniques showed that the Zn foil undergoes dramatic alterations at the surface, which results in inhomogeneous deposition of Zn, whereas the 3D form exhibited minimal changes. Lastly, we paired both Zn foil and 3D Zn with vanadium oxide and demonstrated that the porous structure supports high rate capability and high specific capacity.

25 ENERGY STORAGE↗

Bismuth Electrocatalyst Enabling Reversible Redox Kinetics of a Chelated Chromium Flow Battery Anolyte

Metal electrocatalysts have been reported to improve the electron transfer kinetics of aqueous redox flow battery electrolytes on various types of carbon electrodes. In this work, we electrodeposited bismuth metal onto a carbon paper anode of a redox flow battery containing our previously reported polyaminocarboxylate-chelated chromium electrolyte. Depositing 0.58 mg cm –2 of bismuth metal enabled an electrochemically reversible electron transfer for the Cr(II)/Cr(III) couple, resulting in a 3.9% voltage efficiency increase over ten cycles at 100 mA cm –2 across an 80% state of charge window, while maintaining >99% current efficiency. The bismuth electrocatalyst provided other improvements, such as a 13% increase in average discharge power density when cycling at 80% energy efficiency, along with a 60% decrease in charge transfer resistance and 12% decrease in the full cell area specific resistance. A chelated bismuth complex was also utilized as a bismuth source for electrodeposition, providing an example of how polyaminocarboxylate ligands can be further implemented into efforts towards improving the energy efficiency of aqueous redox flow batteries.

25 ENERGY STORAGE↗

Metallic Cu Surface Enables Reversible Na Metal Anodes and Stabilizes Anode-Free Sodium Metal Batteries

Anode free Na metal batteries are promising for future energy storage because they not only provide the highest energy densities but also eliminate the need of handling hazardous Na metals during battery manufacturing. However, they suffer from much faster degradation due to strong sensitivities even to trace levels of side reactions. In view of the crucial roles of surface chemistry on modulating electrochemical plating, this work systematically investigated a series of Cu surfaces for Na plating and stripping in the 1.0 M NaPF 6 diglyme electrolyte. Our results suggest that Na plating and stripping on pure Cu surface without Cu oxide species exhibits much better reversibility and smaller overpotentials across a wide range of current densities, especially for the first plating/stripping cycle. The high performance includes consistently higher than 99.8% Faradaic efficiencies, much more stable interfacial resistance, and negligible formation of mossy Na after 500 cycles. This improved performance can be explained based on the stronger Na-Cu affinity compared with the Na-CuO affinity. Anode-free Na metal batteries equipped with high-capacity sodium vanadium phosphate cathodes and pure Cu current collector exhibited at least 70% capacity retention for 100 cycles.

Electrochemistry↗