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At least 199 records · Page 11

High-Speed and High-Power Ferroelectric Switching Current Measurement Instrument for Materials with Large Coercive Voltage and Remanent Polarization

A high-speed and high-power current measurement instrument is described for measuring rapid switching of ferroelectric samples with large spontaneous polarization and coercive field. Instrument capabilities (±200 V, 200 mA, and 200 ns order response) are validated with a LiTaO 3 single crystal whose switching kinetics are well known. The new instrument described here enables measurements that are not possible using existing commercial measurement systems, including the observation of ferroelectric switching in large coercive field and large spontaneous polarization Al 0.7 Sc 0.3 N thin films.

30 DIRECT ENERGY CONVERSION↗

Energy Conversion from Heat to Electricity by Highly Reversible Phase-Transforming Ferroelectrics

The search for performant multiferroic materials has attracted general research interest in energy science as they have been increasingly exploited as the conversion media among thermal, electric, magnetic, and mechanical energies by using their temperature-dependent ferroic properties. Here we report a material development strategy that guides us to discover a reversible phase-transforming ferroelectric material exhibiting enduring energy harvesting from small temperature differences. The material satisfies the crystallographic compatibility condition between polar and nonpolar phases, which shows only 2.5°C thermal hysteresis and a high figure of merit. It stably generates 15μA of electricity in consecutive thermodynamic cycles in the absence of any bias fields. We demonstrate our device to consistently generate 6μA/cm 2 current density near 100°C over 540 complete phase transformation cycles without any electric and functional degradation. The energy-conversion device can light up an LED directly without attaching an external power source. Furthermore, this promising material candidate brings the low-grade waste-heat harvesting closer to a practical realization, e.g., small temperature fluctuations around the water boiling point can be considered as a clean energy source.

30 DIRECT ENERGY CONVERSION↗

High‐Performance Al–S Batteries by Spin Polarization Modulation via Catalytic Ni‐MoS 2 Nanosheets

Aluminum–sulfur (Al–S) batteries catalysts with adsorption and catalytic capabilities can effectively improve the slow redox kinetics, but the current research often ignores the effect of optimizing the electronic structure of the catalyst on improving charge transfer and adsorption. Here, in this study, Ni-doped monolayer MoS 2 nanosheets are synthesized and used as a catalytic additive for the sulfur cathode. The addition of Ni promotes spin splitting of 4d orbital of Mo, thereby affecting polarization degree of the basal plane sulfur and making it change from a low spin state to a high spin one. This high spin configuration raises the electron energy level and provides an active electron state to react with aluminum polysulfides (AlPSs), which optimizes the adsorption energy. At the same time, it accelerates electron transfer and lowers the energy barrier for the overall conversion of the polysulfides. Benefiting from these features, Al–S batteries based on rationally designed S@Ni-MoS 2 /C cathodes exhibit a high initial capacity (1603.0 mAh g −1 at 0.5 A g −1 ) and extraordinary cycling stability (0.035% capacity decay rate during 2000 cycles). This study showcases a spin-polarized electronic structure control strategy to enhance catalytic activity, providing a viable approach for developing efficient catalysts for practical Al–S batteries.

Aluminum-sulfur batteries↗

The role of ionic blockades in controlling the efficiency of energy recovery in forward bias bipolar membranes

Limited understanding exists about the operation of bipolar membranes (BPMs) in forward bias to convert protonic gradients into electrical work, despite their emerging role in many electrochemical devices. In these device contexts, the BPM is typically exposed to complex electrolyte mixtures, but their impact on polarization remains poorly understood. Here, for this work, we develop a mechanistic model explaining the forward bias polarization behaviour of BPMs in mixed electrolytes with different acidities/basicities. This model invokes that weak acids/bases accumulate in the BPM and impose an ionic blockade that inhibits the recombination of stronger acids/bases, resulting in a substantial neutralization overpotential. We demonstrate the utility of our model for fuel cells and redox flow batteries and introduce two materials design strategies for mitigating this inhibition. Lastly, we apply our findings to enhance the energy efficiency of carbonate management in CO 2 electrolysers. This work highlights how non-equilibrium local environments at membrane–membrane interfaces can define the efficiency of protonic-to-electrical energy conversion.

25 ENERGY STORAGE↗

Corrosion Studies of 2195 Al-Li Alloy and 2219 Al Alloy with Differing Surface Treatments

Corrosion studies of 2195 Al-Li and 2219 Al alloys have been conducted using the scanning reference electrode technique (SRET) and the polarization resistance (PR) technique. The SRET was used to study corrosion mechanisms, while corrosion rate measurements were studied with the PR technique. Plates of Al203 blasted, soda blasted and conversion coated 2219 Al were coated with Deft primer and the corrosion rates studied with the EIS technique. Results from all of these studies are presented.

Danford, M. D.↗

Inverse Consequences of the SnO 2 Protection Layers on Pt/C Catalysts in Proton-Exchange Membrane Fuel Cells

Proton-exchange membrane fuel cells (PEMFCs) are promising energy-conversion systems, offering an appealing blend of high energy efficiency and low environmental impact. However, carbon corrosion of PEMFCs is known to significantly degrade their performance, remaining a critical challenge to overcome. In this study, we applied a Nb-doped SnO 2 (Nb-SnO 2 ) nanoparticle coating on Pt/C catalysts as a protective layer, with the Sn/C ratio in the precursors varying from 0.25:1 to 2.0:1. Contradictory behaviors of the coated Pt/C catalysts were observed at different Sn/C ratios. The Sn/C = 1.0 sample exhibited improved electrochemically active surface area retention after 500 cycles of accelerated stress testing (AST) but with more significant polarization and resistance increase observed in the polarization curves. In addition, agglomeration of Nb-SnO 2 particles was observed at a higher Sn/C ratio in the AST of a membrane electrode assembly, with less shrinkage of the total thickness of the Nb-SnO 2 -coated Pt/C electrode. We speculate that formation of Nb-SnO 2 agglomerates occurs once the protective layer is broken down or the unprotected carbon surface is corroded and that these Nb-SnO 2 agglomerates increase the tortuosity of the electron pathways and significantly increase the cell polarization.

30 DIRECT ENERGY CONVERSION↗

Symmetry-Breaking Charge Transfer in Metal–Organic Frameworks

High quantum-yield charge carrier generation from the initially prepared excitons defines a key step in the light-harvesting and conversion scheme. Photoinduced charge transfer in molecular electron donor—acceptor assemblies is driven by a sizable ΔG 0 , which compromises the potential of the generated carriers. Reminiscent of the special pair at the reaction center of the natural light-harvesting complex, symmetry-breaking charge transfer (SBCT) within a pair of identical struts of metal-organic framework (MOF) will facilitate the efficient generation of long-lived charge carriers with maximized potentials without incorporating any foreign redox species. We report SBCT in pyrene-based zirconium metal–organic framework (MOF) NU-1000 that leads to efficient generation of radical ions in a polar solvent and bound CT states in a low-polar solvent. Further, the probe unveils the role of the low-lying non-Franck–Condon excitonic states as intermediates in the formation of the SBCT state from the initially prepared Franck–Condon S 1 states. Ultrafast and transient spectroscopy—probed over 200 fs-30 μs time scale-evinces a k SBCT = (110 ps) -1 in polar media (ε s = 37.5) forming solvated radical ions with recombination rate k CR = (~45 ns) -1 . A slower rate with k SBCT = (203 ps) -1 was recorded in low-polar (ε s = 7.0) solvent manifesting a bound [TBAPy •+ TBAPy •– ] state with k CR ≈ (17 μs) -1 . This discovery, along with other unique photophysical features relevant to light harvesting, should define a MOF-based platform for developing heterogeneous artificial photon energy conversion systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Relativistic electromagnetic waves in an electron-ion plasma

High power laser beams can drive plasma particles to relativistic energies. An accurate description of strong waves requires the inclusion of ion dynamics in the analysis. The equations governing the propagation of relativistic electromagnetic waves in a cold electron-ion plasma can be reduced to two equations expressing conservation of energy-momentum of the system. The two conservation constants are functions of the plasma stream velocity, the wave velocity, the wave amplitude, and the electron-ion mass ratio. The dynamic parameter, expressing electron-ion momentum conversation in the laboratory frame, can be regarded as an adjustable quantity, a suitable choice of which will yield self-consistent solutions when other plasma parameters were specified. Circularly polarized electromagnetic waves and electrostatic plasma waves are used as illustrations.

Chian, Abraham C.-L.↗

The Advanced Energetic Pair Telescope (AdEPT}: A Future Medium-Energy Gamma-Ray Balloon (and Explorer?) Mission

Gamma-ray astrophysics probes the highest energy, exotic phenomena in astrophysics. In the medium-energy regime, 0.1-200 MeV, many astrophysical objects exhibit unique and transitory behavior such as the transition from electron dominated to hadron dominated processes, spectral breaks, bursts, and flares. Medium-energy gamma-ray imaging however, continues to be a major challenge particularly because of high background, low effective area, and low source intensities. The sensitivity and angular resolution required to address these challenges requires a leap in technology. The Advance Energetic Pair Telescope (AdEPT) being developed at GSFC is designed to image gamma rays above 5 MeV via pair production with angular resolution of 1-10 deg. In addition AdEPT will, for the first time, provide high polarization sensitivity in this energy range. This performance is achieved by reducing the effective area in favor of enhanced angular resolution through the use of a low-density gaseous conversion medium. AdEPT is based on the Three-Dimensional Track Imager (3-DTI) technology that combines a large volume Negative Ion Time Projection Chamber (NITPC) with 2-D Micro-Well Detector (MWD) readout. I will review the major science topics addressable with medium-energy gamma-rays and discuss the current status of the AdEPT technology, a proposed balloon instrument, and the design of a future satellite mission.

Hunter, Stanley D.↗

Joint influence of γ–irradiation and high temperature shear grinding on the IR spectra and surface–energy properties of polyethylene

The optical and surface-energy properties of polyethylene (PE) subjected to γ-irradiation and post-radiation, high temperature, shear grinding are presented. Comparison of the IR spectra of the initial and γ-irradiated PE shows that oxygen-containing groups and unsaturated bonds in the polymer macromolecules are formed and accumulate during their radiolysis in air, increasing with γ-irradiation dose. A redistribution of the products of radiation-chemical conversion on the surface of the polymer granules throughout the entire volume of the powder occurs after high-temperature shear milling to a powder as observed in the IR spectrum. Polar functional groups due to oxidation reactions are observed on the surface layer of the sample after post-radiation grinding. Furthermore, the initial polymer surface is weakly basic with an acidity parameter of -0.34. The value of the acidity parameter of the sample made of ground irradiated PE has an acidic surface with an acidity parameter of 0.65. γ irradiation of the secondary processing of PE waste with high-temperature shear grinding is a promising approach to obtain a secondary PE powder with specified parameters and different degrees of functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing Interactions between Adsorbed Polymers and γ-Al 2 O 3 Using Solid-State NMR

The interactions between polymers and metal oxide surfaces affect the physical properties of polymer composites and the selectivity of catalysts used for plastic conversion. Gauging the strengths of these interactions and how they depend on adsorption conformations and polymer structure is nevertheless quite challenging. Herein, we evaluate whether a recently introduced dynamic nuclear polarization-based surface-to-atom distance measurement method can be used to gauge the specific interactions between five vinyl polymers and an oxide support (alumina). The adsorption conformations of polymer monolayers were studied using site-specific 13 C{ 27 Al} rotational-echo saturation-pulse double-resonance (RESPDOR) experiments. The method is effective in revealing the average distance between the adsorbed polymer and the surface, as well as the fraction of the monomers that are adsorbed. Polymers that possess larger side chains are more weakly adsorbed, as evidenced by their formation of more numerous loop and tail structures. In conclusion, the measured RESPDOR dephasing data further reveals that polymer adsorption conformations are largely disordered and involve few hydrogen bonding interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Lignin Solubility and Structure in Organic Solvents

Lignin, a polymer found in the secondary plant cell wall of terrestrial plants, is the single largest source of renewable aromatics and has attracted considerable attention as a feedstock for potential industrial use. However, the secondary plant cell wall is a crowded environment, and lignin in its native form interacts with other biomass components within a larger network. Application of some organic solvents is known to liberate lignin from this network and creates lignin-rich streams suitable for conversion into target products. Through molecular-scale lignin simulation, we analyze how diverse lignin polymers change their structure in response to varying organic solvent environments. We quantify the relationship between solvent polarity and lignin polymer extension, observing maximum polymer expansion and solvation for solvents with polarity near those of dimethyl sulfoxide. From our observations at the nanoscale, increasing syringyl content within lignin polymers reduces the expansion of the polymer in organic solvent environments and decreases the free energy difference compared to aqueous solvent environments, thereby reducing solubility for high syringyl lignin polymers. The conformational transition rates between lignin polymer shapes increased through a combination of the solvent diffusion constant and polymer extension. The molecular simulations indicate that there is likely no single optimal organic solvent for lignin. Different solvent mixtures have optimal or near-optimal properties in solubilizing lignin polymers, thereby disrupting interactions with other biopolymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydration Mechanisms in Nanoparticle Interaction and Surface Energetics

Work on the project advanced molecular level understanding, prediction and control of nanoscale hydration in salt solutions under electric stimuli or ionic patterning. Permeation of nanoporous electrodes at preset voltage underlies the function of ultracapacitors. Transitory regulation of wetting in nanoporous media by electric field spans an array of applications in materials, energy storage, and separation sciences. The physically related modulation of nanoparticle solubility by surface charges can significantly extend the range of the nanomaterial applications, improve processing techniques, and potentially alleviate environmental concerns. Pore/solution equilibria, and activated kinetics of liquid gating by nanoconfined electrolytes are challenging problems at the forefront of experimental and theoretical research. Addressing these problems from a molecular perspective required the development of state-of-the-art simulation algorithms in statistical mechanics to capture complex processes in open systems under electric control. Parallel studies of wetting and dispersibility of polar and ionizing particles aim to uncover predictive relations between electrowetting, chemical functionalization, and geometry of nanomaterial particles. By nonequilibrium dynamic modeling, we elucidated electrolyte flow in nanochanels and associated electrokinetic energy conversion. Research on the program provided training opportunities for the next generation of scientists in computational chemistry. Insights, and methods from the project implicate broad segment of researchers in energy and nanosciences, materials and surface chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗

Surfactant-assisted liquefaction of particulate carbonaceous substances

A slurry of carbonaceous particles such as coal containing an oil soluble polar substituted oleophilic surfactant, suitably an amine substituted long chain hydrocarbon, is liquefied at high temperature and high hydrogen presence. The pressure of surfactant results in an increase in yield and the conversion product contains a higher proportion of light and heavy oils and less asphaltene than products from other liquefaction processes.

Hsu, G. C.↗

AMEGO: Exploring the Extreme Multimessenger Universe

The All-sky Medium Energy Gamma-ray Observatory (AMEGO) is a Probe-class mission concept that will provide essential contributions to multimessenger astrophysics in the next decade. AMEGO operates both as a Compton and pair telescope to achieve unprecedented sensitivity between 200 keV and>5 GeV. The instrument consists of four subsystems. A double-sided strip silicon Tracker gives a precise measure of the first Compton scatter interaction and tracks of pair-conversion products. A novel CdZnTe Low Energy Calorimeter with excellent position and energy resolution surrounds the bottom and sides of the Tracker to detect the Compton-scattered photons which enhances the polarization and narrow-line sensitivity. A thick CsI High Energy Calorimeter contains the high-energy Compton and pair events. The instrument is surrounded by aplastic anti-coincidence detector to veto the cosmic-ray background. We have performed detailed simulations to predict the telescope performance and are currently building a prototype instrument. The AMEGO prototype, known as ComPair, will be tested at the High Intensity Gamma-Ray Source in 2021, followed by a balloon flight in Fall of 2022. In this presentation we will give an overview of the science motivation, a description of the observatory, and an update of the prototype instrument development.

Carolyn Ann Kierans↗

Barotropic instability of basic states with a realistic jet and a wave

The stability of basic states consisting of a jet similar to the stratospheric polar night jet and a traveling wave with a single zonal wavenumber is examined in a linearized nondivergent barotropic model on a sphere. Basic state waves are chosen to resemble observed traveling and stationary features in the winter stratosphere. Results are presented for disturbance growth rates, propagation characteristics, and energy conversion as a function of the basic state wave amplitude. The effects of small amplitude basic state waves on unstable disturbances arising from a zonally symmetric jet are discussed; results are shown where a small amplitude basic state wave dramatically affects the stability characteristics. Evidence is shown that the presence of a traveling wave may favor the appearance of disturbances that include other zonal wavenumbers which move with the basic state wave; this result is discussed in relation to the origin of observed quasi-nondispersive features in the polar winter stratosphere. Results for a stationary wavenumber 1 basic state wave suggest that a distorted polar vortex may be unstable to disturbances that would lead to further distortion. An unstable disturbance for a basic state with an eastward moving wavenumber 2 has components which resemble, in period and location, traveling waves that are observed in the winter stratosphere.

Manney, Gloria L.↗

Multi-Wavelength, Multi-Beam, and Polarization-Sensitive Laser Transmitter for Surface Mapping

A multi-beam, multi-color, polarized laser transmitter has been developed for mapping applications. It uses commercial off-the-shelf components for a lowcost approach for a ruggedized laser suitable for field deployment. The laser transmitter design is capable of delivering dual wavelengths, multiple beams on each wavelength with equal (or variable) intensities per beam, and a welldefined state of polarization. This laser transmitter has been flown on several airborne campaigns for the Slope Imaging Multi-Polarization Photon Counting Lidar (SIMPL) instrument, and at the time of this reporting is at a technology readiness level of between 5 and 6. The laser is a 1,064-nm microchip high-repetition-rate laser emitting energy of about 8 microjoules per pulse. The beam was frequency-doubled to 532 nm using a KTP (KTiOPO4) nonlinear crystal [other nonlinear crystals such as LBO (LiB3O5) or periodically poled lithium niobiate can be used as well, depending on the conversion efficiency requirements], and the conversion efficiency was approximately 30 percent. The KTP was under temperature control using a thermoelectric cooler and a feedback monitoring thermistor. The dual-wavelength beams were then spectrally separated and each color went through its own optical path, which consisted of a beam-shaping lens, quarterwave plate (QWP), and a birefringent crystal (in this case, a calcite crystal, but others such as vanadate can be used). The QWP and calcite crystal set was used to convert the laser beams from a linearly polarized state to circularly polarized light, which when injected into a calcite crystal, will spatially separate the circularly polarized light into the two linear polarized components. The spatial separation of the two linearly polarized components is determined by the length of the crystal. A second set of QWP and calcite then further separated the two beams into four. Additional sets of QWP and calcite can be used to further split the beams into multiple orders of two. The spatially separated beams had alternating linearly polarization states; a half-wave plate (HWP) array was then made to rotate the alternating states of A multi-beam, multi-color, polarized laser transmitter has been developed for mapping applications. It uses commercial off-the-shelf components for a lowcost approach for a ruggedized laser suitable for field deployment. The laser transmitter design is capable of delivering dual wavelengths, multiple beams on each wavelength with equal (or variable) intensities per beam, and a welldefined state of polarization. This laser transmitter has been flown on several airborne campaigns for the Slope Imaging Multi-Polarization Photon Counting Lidar (SIMPL) instrument, and at the time of this reporting is at a technology readiness level of between 5 and 6. The laser is a 1,064-nm microchip high-repetition-rate laser emitting energy of about 8 microjoules per pulse. The beam was frequency-doubled to 532 nm using a KTP (KTiOPO4) nonlinear crystal [other nonlinear crystals such as LBO (LiB3O5) or periodically poled lithium niobiate can be used as well, depending on the conversion efficiency requirements], and the conversion efficiency was approximately 30 percent. The KTP was under temperature control using a thermoelectric cooler and a feedback monitoring thermistor. The dual-wavelength beams were then spectrally separated and each color went through its own optical path, which consisted of a beam-shaping lens, quarterwave plate (QWP), and a birefringent crystal (in this case, a calcite crystal, but others such as vanadate can be used). The QWP and calcite crystal set was used to convert the laser beams from a linearly polarized state to circularly polarized light, which when injected into a calcite crystal, will spatially separate the circularly polarized light into the two linear polarized components. The spatial separation of the two linearly polarized components is determined by the length of the crystal. A cond set of QWP and calcite then further separated the two beams into four. Additional sets of QWP and calcite can be used to further split the beams into multiple orders of two. The spatially separated beams had alternating linearly polarization states; a half-wave plate (HWP) array was then made to rotate the alternating states of

Yu, Anthony W.↗

Preparation of a uranium monocarbide anode and electrochemical characterization in molten LiCl-KCl-UCl 3

Porous uranium carbide (UC) pellets possessing moderate electrical conductivity were synthesized by reaction of UO 2 with graphite at temperatures up to 1550°C under rough vacuum. Conversions as high as 98% were achieved at soak times of 2-4 hours. The electrochemistry of the UC pellets in molten LiCl-KCl-6.5 wt% UCl 3 was explored using a variety of techniques including DC polarization methods, cyclic voltammetry, chronopotentiometry and bulk electrolysis. Here, the electrode reaction for anodic dissolution was found to be kinetically controlled by dissociation of UC to a transition state complex that was hypothesized to consist of a uranium atom partially complexed by chloride ions. Precise measurements of current efficiencies using chronopotentiometry indicated upper limits of 90.9 ± 3.4% and 98.3 +1.7/-3.7% for anode and cathode, respectively, when operating at anodic overpotentials near +300 mV. Bulk electrolysis of a UC pellet performed by passing 98% of the theoretical charge resulted in nearly complete recovery of its uranium content as highly pure metal at the cathode.

36 MATERIALS SCIENCE↗