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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Binary neutron star mergers as a probe of quark-hadron crossover equations of state

It is anticipated that the gravitational radiation detected in future gravitational wave (GW) detectors from binary neutron star (NS) mergers can probe the high-density equation of state (EOS). In this work, we perform the first simulations of binary NS mergers which adopt various parametrizations of the quark-hadron crossover (QHC) EOS. These are constructed from combinations of a hadronic EOS ($n_b$<2 $n_0$) and a quark-matter EOS ($n_b$>5 $n_0$), where $n_b$ and $n_0$ are the baryon number density and the nuclear saturation density, respectively. At the crossover densities (2 $n_0$ < $n_b$ < 5 $n_0$) the QHC EOSs continuously soften, while remaining stiffer than hadronic and first-order phase transition EOSs, achieving the stiffness of strongly correlated quark matter. This enhanced stiffness leads to significantly longer lifetimes of the postmerger NS than that for a pure hadronic EOS. We find a dual nature of these EOSs such that their maximum chirp GW frequencies $f_{\text{max}}$ fall into the category of a soft EOS while the dominant peak frequencies ($f_{\text{peak}}$) of the postmerger stage fall in between that of a soft and stiff hadronic EOS. An observation of this kind of dual nature in the characteristic GW frequencies will provide crucial evidence for the existence of strongly interacting quark matter at the crossover densities for QCD.

79 ASTRONOMY AND ASTROPHYSICS↗

Three Jahn-Teller States of Matter in Spin-Crossover System Mn(taa)

Three high-spin phases recently discovered in the spin-crossover system Mn(taa) are identified through analysis by a combination of first-principles calculations and Monte Carlo simulation as a low-temperature Jahn-Teller ordered (solid) phase, an intermediate-temperature dynamically correlated (liquid) phase, and an uncorrelated (gas) phase. In particular, the Jahn-Teller liquid phase arises from competition between mixing with low-spin impurities, which drive the disorder, and intermolecular strain interactions. Additionally, the latter are a key factor in both the spin-crossover phase transition and the magnetoelectric coupling. Jahn-Teller liquids may exist in other spin-crossover materials and materials that have multiple equivalent Jahn-Teller axes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Generalized susceptibilities and the properties of charm degrees of freedom across the QCD crossover temperature

We study the generalized charm susceptibilities in 2+1 flavor QCD on the lattice at several lattice spacings. We show that, below the chiral crossover, these susceptibilities are well described by the hadron resonance gas (HRG) model if charmed hadrons not listed in tables of the Particle Data Group are included. However, the HRG description abruptly breaks down just above the chiral crossover. To understand this, we use a model for the charm pressure in which it is expressed as the sum of partial pressures from charmed baryons, charmed mesons, and charm quarks. We present continuum estimates of these partial pressures and find that, while the partial pressures of charmed mesons and baryons drop below their respective HRG predictions, the charm quark pressure becomes nonzero above the chiral crossover.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Crossover between strongly coupled and weakly coupled exciton superfluids

Following a crossover Superfluidity in fermionic systems occurs through the pairing of fermions into bosons, which can undergo condensation. Depending on the strength of the interactions between fermions, the pairs range from large and overlapping to tightly bound. The crossover between these two limits has been explored in ultracold Fermi gases. Liu et al . observed the crossover in an electronic system consisting of two layers of graphene separated by an insulating barrier and placed in a magnetic field. In this two-dimensional system, the pairs were excitons formed from an electron in one layer and a hole in the other. The researchers used magnetic field and layer separation to tune the interactions and detected the signatures of superfluidity through transport measurements. —JS

Science & Technology - Other Topics↗

Quantum phase crossover in the spherical mean-field plus quadrupole–quadrupole and pairing model with two j-orbits

The shape phase crossover in the mean-field plus the geometric quadrupole–quadrupole and pairing model within two [Formula: see text]-orbits is analyzed, for which a simple description of [Formula: see text]Sn confined in the lowest [Formula: see text] and [Formula: see text] orbits above the [Formula: see text]Sn core is demonstrated to reveal the crossover behavior of the model. It is shown that [Formula: see text], [Formula: see text] and [Formula: see text], [Formula: see text] in this case may serve as effective order parameters for even–even and odd-A systems, respectively, from which the shape phase crossover from the rotation-like phase to the superconducting-like phase can be observed with variation of the number of valence neutrons.

Physics↗

Near‐Room‐Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex

Abstract Magnetoelectric coupling is achieved near room temperature in a spin crossover Fe II molecule‐based compound, [Fe(1bpp) 2 ](BF 4 ) 2 . Large atomic displacements resulting from Jahn–Teller distortions induce a change in the molecule dipole moment when switching between high‐spin and low‐spin states leading to a step‐wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3–0.4 mC m −2 changes in the H ‐induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Innovative duo-recombination layer design for effective hydrogen crossover mitigation in advanced MEAs for PEM water electrolyzers

Hydrogen crossover in proton exchange membrane water electrolyzers (PEMWEs) poses a safety hazard, reduces the overall efficiency, and limits the operational differential pressure range. Here, in this study, a membrane electrode assembly (MEA) with innovative Pt duo-recombination layer (DRL) design is developed by the unique reactive spray deposition technology (RSDT). The novel design comprises two thin RLs integrated within the volume of the membrane and has a total Pt loading of only 0.04 mg Pt cm −2 . Long-term durability test for over 3000 h is performed with as-fabricated MEA at steady-state conditions typical for an industrial hydrogen production system. The results from the durability test show that the newly developed DRL design effectively suppresses the H2 crossover to below 0.5 vol%. Furthermore, comprehensive post-test characterization of the MEA is performed and potential failure mechanisms in the Pt RLs observed during the durability test are identified and discussed in detail for the first time.

08 HYDROGEN↗

Single-layer graphene as a highly selective barrier for vanadium crossover with high proton selectivity

In this paper, we report near-zero crossover for vanadium cross-permeation through single-layer graphene immobilized at the interface of two Nafion® polymer electrolyte membranes. Vanadium ion diffusion and migration, including proton mobility through membrane composites, were studied with and without graphene under diffusion and migration conditions. Single-layer graphene was found to effectively inhibit vanadium ion diffusion and migration under specific conditions. The single-layer graphene composites also enabled remarkable ion transmission selectivity improvements over pure Nafion® membranes, with proton transport being four orders of magnitude faster than vanadium ion transport. Resistivity values of 0.02 ± 0.005 Ω cm 2 for proton and 223 ± 4 Ω cm 2 for vanadium ion through single atomic layer graphene are reported. This high selectivity may have significant impact on flow battery applications or for other electrochemical devices where proton conductivity is required, and transport of other species is detrimental. Our results emphasize that crossover may be essentially completely eliminated in some cases, enabling for greatly improved operational viability.

2D nanomaterial↗

Membrane–Electrolyte System Approach to Understanding Ionic Conductivity and Crossover in Alkaline Flow Cells

Membrane transport properties are crucial for electrochemical devices, and these properties are influenced by the composition and concentration of the electrolyte in contact with the membrane. We apply this general membrane-electrolyte system approach to alkaline flow batteries, studying conductivity and ferricyanide crossover of Nafion and E-620. We report undetectable crossover for as-received Nafion and E-620 after both sodium and potassium exchange, but high ferricyanide permeability of 10 –7 to 10 –8 cm2 s –1 for Nafion subjected to pre-treatment prevalent in the flow battery literature. We show how the electrolyte mass fraction in hydrated membranes regulates the influence of ion concentration on membrane conductivity, identifying that increasing electrolyte concentration may not increase 1 membrane conductivity even when it increases electrolyte conductivity. To illustrate this behavior we introduce a new metric, the membrane penalty, as the ratio of the conductivity of the electrolyte to that of the membrane equilibrated with the electrolyte. We discuss the tradeoff between flow battery volumetric capacity and areal power density that arises from these findings. Finally, we apply insights from this approach to provide recommendations for use of membranes in alkaline flow cells, and electrochemical reactors in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane-Induced Vanadium Crossover-Blocking Polybenzimidazole Copolymer with Exceptional Proton Selectivity

Broad deployment of redox flow batteries is hindered, in part, due to the lack of highly selective ion-exchange membranes with high proton conductivity. We report a post-functionalization strategy for polybenzimidazole copolymer (PBI-co) membranes by a reacting mixture of concentrated sulfuric and phosphoric acids that led to improved membrane selectivity while retaining high proton conductivity. Fourier-transform infrared spectroscopy confirmed successful sulfonation and protonation of benzimidazole functionalities. PBI-co exhibits a very high room-temperature proton conductivity of 0.138 S cm -1 , as measured by electrochemical impedance spectroscopy. PBI-co also demonstrates electromigration crossover mitigation under applied current densities up to 500 mA cm -2 , and voltage pulses up to 1.4 V, while also inhibiting diffusion-driven vanadium crossover for over 20 days. Single-cell vanadium flow battery testing on post-functionalized PBI-co further confirms state-of-the-art battery performance with an ~99.5% Coulombic efficiency at 100 mA cm -2 and an area-specific resistance of ~20 mO cm 2 lower than Nafion-212 membrane.

25 ENERGY STORAGE↗

Crossover from quantum to classical transport

Understanding the crossover from quantum to classical transport phenomena has become of fundamental importance not only for technological applications due to the creation of sub-10nm transistors – an important building block of our modern life – but also for elucidating the role played by quantum mechanics in the evolutionary fitness of biological complexes. This article provides a basic introduction into the nature of charge and energy transport in the quantum and classical regimes. Here, it will identify the characteristic transport properties in both limits, and demonstrate how they can be connected through the loss of quantum mechanical coherence. I will identify the salient features of the crossover physics, and demonstrate their importance in opening new transport regimes and for understanding efficient and robust energy transport in biological complexes.

charge↗

Hydrogen Crossover Flux through Two-Dimensional Nanomaterials

Energy storage and conversion devices require an ion-exchange membrane with high transmission of charge-balancing ions and separation of anode and cathode electrolytes/gases. This ensures optimum device performance. Most conventional membranes suffer huge cross-permeation resulting in low energy efficiency and material degradation. This work investigated hydrogen permeability and proton transmission through membrane electrode assemblies (MEAs) containing a monolayer of hexagonal boron nitride and single-layer and bi-layer graphene in a gas-phase small-scale cell and a liquid cell. Here we found that the hydrogen crossover flux through MEAs with 2D materials was inhibited by at least a factor of 5 compared to the one without. Single-layer graphene and boron nitride enabled high proton transmission, but bi-layer graphene inhibited proton conduction. Defect visualization of 2D materials revealed few atomic-scale defects in graphene. These findings suggest that a monolayer of 2D material may provide good selectivity for energy conversion and storage devices by blocking species crossover while allowing high proton transmission.

2D materials↗

Advanced PEM Electrolyzer Membrane for Hydrogen Crossover Mitigation

An unintended reaction in the electrochemical conversion of water to hydrogen in proton exchange membrane (PEM) electrolyzers is the crossover of hydrogen from the anode to the oxygen-containing cathode through the membrane, creating hydrogen losses and safety concerns. Efforts to date have focused on embedding platinum catalysts in perfluorosulfonic (PFSA) membranes to convert H 2 to protons. The objective of this project is to design and develop hydrocarbon (HC) proton exchange membranes (PEMs) that can help overcome the risk of high H 2 crossover in current PEM electrolyzer (ELX) stacks by designing and optimizing the gas recombination catalyst (GRC) within the membrane and membrane electrode assembly (MEA) structure.

08 HYDROGEN↗

Crossover Effects of Transition‐Metal Ions on Lithium‐Metal Anode in Localized High Concentration Electrolytes

Abstract The stability of the solid–electrolyte interphase (SEI) is critical to the cycle life of lithium‐metal batteries (LMBs). While the crossover effect of transition‐metal ions from cathode to anode is extensively studied in lithium‐ion batteries with graphite anodes, its impact on LMBs remains largely unexplored. Herein, this study investigates the electrochemical and chemical properties of SEI layers formed on lithium‐metal anodes in localized high‐concentration electrolytes (LHCEs) containing dissolved transition‐metal ions (Ni 2+ , Mn 2+ , and Co 2+ ). It is demonstrated that transition‐metal ions in LHCEs reduce the coulombic efficiency (CE) and significantly degrade the cycle life of LMBs. Time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) reveals that SEI structures differ depending on the dissolved TM ion, with Mn 2+ and Co 2+ inducing severe destabilization, and Ni 2+ exhibiting a less severe impact. These findings underscore the detrimental effects of transition‐metal crossover effects in LMB systems.

Guo, Zezhou [Materials Science and Engineering Pro↗

Stress‐Induced Domain Wall Motion in a Ferroelastic Mn 3+ Spin Crossover Complex

Abstract Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single‐crystal X‐ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn 3+ compound [Mn(3,5‐diBr‐sal 2 (323))]BPh 4 , 1. The first at 250 K, involves the space group change Cc → Pc and is thermodynamically continuous, while the second, Pc → P 1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress‐induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc ‐ P 1 transition

Jakobsen, Vibe B.↗

Near‐Room‐Temperature Magnetoelectric Coupling via Spin Crossover in an Iron(II) Complex

Abstract Magnetoelectric coupling is achieved near room temperature in a spin crossover Fe II molecule‐based compound, [Fe(1bpp) 2 ](BF 4 ) 2 . Large atomic displacements resulting from Jahn–Teller distortions induce a change in the molecule dipole moment when switching between high‐spin and low‐spin states leading to a step‐wise change in the electric polarization and dielectric constant. For temperatures in the region of bistability, the changes in magnetic and electrical properties are induced with a remarkably low magnetic field of 3 T. This result represents a successful expansion of magnetoelectric spin crossovers towards ambient conditions. Moreover, the observed 0.3–0.4 mC m −2 changes in the H ‐induced electric polarization suggest that the high strength of the coupling obtained via this route is accessible not just at cryogenic temperatures but also near room temperature, a feature that is especially appealing in the light of practical applications.

Owczarek, Magdalena↗

Motion of a viscous slug on heterogeneous surfaces: crossover from stick–slip to steady sliding

We present a theoretical study of viscous slug motion inside a microscopically rough capillary tube, where pronounced stick–slip motion can emerge at slow displacement rates. The mathematical description of this intermittent motion can be reduced to a system of ordinary differential equations, which also describe the motion of a pendulum inside a fluid-filled rotating drum. We use this analogy to show that the stick–slip motion transitions to steady sliding at high displacement rates. We characterize this crossover with a simple scaling relation and show that the crossover is accompanied by a shift in the dominant energy dissipation mechanisms within the system.

Mechanics↗

Crossover from Rouse to Reptation Dynamics in Salt-Free Polyelectrolyte Complex Coacervates

Considerable interest in the dynamics and rheology of polyelectrolyte complex coacervates has been motivated by their industrial application as viscosity modifiers. A central question is the extent to which classical Rouse and reptation models can be applied to systems where electrostatic interactions play a critical role on the thermodynamics. By relying on molecular simulations, we present a direct analysis of the crossover from Rouse to reptation dynamics in salt-free complex coacervates as a function of chain length. This crossover shifts to shorter chain lengths as electrostatic interactions become stronger, which corresponds to the formation of denser coacervates. To distinguish the roles of Coulomb interactions and density, here we compare the dynamics of coacervates to those of neutral, semidilute solutions at the same density. Both systems exhibit a universal dynamical behavior in the connectivity-dominated (subdiffusion and normal diffusion) regimes, but the monomer relaxation time in coacervates is much longer and increases with increasing Bjerrum length. This is similar to the cage effect observed in glass-forming polymers, but the local dynamical slowdown is caused here by strong Coulomb attractions (ion pairing) between oppositely charged monomers. Our findings provide a microscopic framework for the quantitative understanding of coacervate dynamics and rheology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗