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At least 595 records · Page 33

Helical Complex Ladder Polymer with Amplification of Asymmetry

Here, we report a Cu–salen helical complex ladder polymer (HLP-Cu) built from covalently fused Cu(Salen) units. Point chirality from enantiopure diamines directs the formation of a rigid, π-conjugated helix. Compared with a planar analogue (LLP-Cu) and the Cu(Salen) monomer, HLP-Cu exhibits up to 5-fold stronger circular dichroism and a maximum dissymmetry factor of 7.4 × 10 –3 . Titration experiments suggest a cooperative amplification of asymmetry arising from extended conjugation and helical geometry during helix formation. Time-dependent density functional theory calculations are employed to support this hypothesis, showing that increasing conjugation length and helical order enhance the rotational strength of contributing excited states via elevated magnetic transition moments and improved alignment of electric and magnetic transition moments. Our findings provide a new polymer platform for designing functional chiral materials with tunable chiroptical and spin-dependent properties.

36 MATERIALS SCIENCE↗

Electrode Blocking Due to Redox Reactions in Aluminum Chloride-Sodium Iodide Molten Salts

Iodide redox reactions in molten NaI/AlCl 3 are shown to generate surface-blocking films, which may limit the useful cycling rates and energy densities of molten sodium batteries below 150 °C. An experimental investigation of electrode interfacial stability at 110 °C reveals the source of the reaction rate limitations. Electrochemical experiments in a 3-electrode configuration confirm an increase of resistance on the electrode surface after oxidation or reduction current is passed. Using chronopotentiometry, chronoamperometry, cyclic voltammetry, and electrochemical impedance spectroscopy, the film formation is shown to depend on the electrode material (W, Mo, Ta, or glassy carbon), as well as the Lewis acidity and molar ratio of I − /I 3 − in the molten salt electrolytes. These factors impact the amount of charge that can be passed at a given current density prior to developing excessive overpotential due to film formation that blocks the electrode surface. The results presented here guide the design and use of iodide-based molten salt electrolytes and electrode materials for grid scale battery applications.

25 ENERGY STORAGE↗

Global Simulation of Electromagnetic Ion Cyclotron Waves

It is well known that the effects of electromagnetic ion cyclotron (EMIC) waves on ring current (RC) ion and radiation belt (RB) electron dynamics strongly depend on such particle/wave characteristics as the phase-space distribution function, frequency, wave-normal angle, wave energy, and the form of wave spectral energy density. The consequence is that accurate modeling of EMIC waves and RC particles requires robust inclusion of the interdependent dynamics of wave growth/damping, wave propagation, and particles. Such a self-consistent model is being progressively developed by Khazanov et al. [2002 - 2007]. This model is based on a system of coupled kinetic equations for the RC and EMIC wave power spectral density along with the ray tracing equations. We will discuss the recent progress in understanding EMIC waves formation mechanisms in the inner magnetosphere. This problem remains unsettled in spite of many years of experimental and theoretical studies. Modern satellite observations by CRRES, Polar and Cluster still do not reveal the whole picture experimentally since they do not stay long enough in the generation region to give a full account of all the spatio-temporal structure of EMIC waves. The complete self-consistent theory taking into account all factors significant for EMIC waves generation remains to be developed. Several mechanisms are discussed with respect to formation of EMIC waves, among them are nonlinear modification of the ionospheric reflection by precipitating energetic protons, modulation of ion-cyclotron instability by long-period (Pc3/4) pulsations, reflection of waves from layers of heavy-ion gyroresonances, and nonlinearities of wave generation process. We show that each of these mechanisms have their attractive features and explains certain part experimental data but any of them, if taken alone, meets some difficulties when compared to observations. We conclude that development of a refined nonlinear theory and further correlated analysis of modern satellite and ground-based data is needed to solve this very intriguing problem.

Khazanov, G. V.↗

Global Simulation of Electromagnetic Ion Cyclotron Waves

It is very well known that the effects of electromagnetic ion cyclotron (EMIC) waves on ring current (RC) ion and radiation belt (RB) electron dynamics strongly depend on such particle/wave characteristics as the phase-space distribution function, frequency, wave-normal angle, wave energy, and the form of wave spectral energy density. The consequence is that accurate modeling of EMIC waves and RC particles requires robust inclusion of the interdependent dynamics of wave growth/damping, wave propagation, and particles. Such a self-consistent model is being progressively developed by Khazanov et al. This model is based on a system of coupled kinetic equations for the RC and EMIC wave power spectral density along with the ray tracing equations. We will discuss the recent progress in understanding EMIC waves formation mechanisms in the inner magnetosphere. This problem remains unsettled in spite of many years of experimental and theoretical studies. Modern satellite observations by CRRES, Polar and Cluster still do not reveal the whole picture experimentally since they do not stay long enough in the generation region to give a full account of all the spatio-temporal structure of EMIC waves. The complete self-consistent theory taking into account all factors significant for EMIC waves generation remains to be developed. Several mechanisms are discussed with respect to formation of EMIC waves, among them are nonlinear modification of the ionospheric reflection by precipitating energetic protons, modulation of ion-cyclotron instability by long-period (Pc3/4) pulsations, reflection of waves from layers of heavy-ion gyroresonances, and nonlinearities of wave generation process. We show that each of these mechanisms have their attractive features and explains certain part experimental data but any of them, if taken alone, meets some difficulties when compared to observations. We conclude that development of a refined nonlinear theory and further correlated analysis of modern satellite and ground-based data is needed to solve this very intriguing problem.

Khazanov, George V.↗

Smoke, Clouds, and Radiation-Brazil (SCAR-B) Experiment

The Smoke, Clouds, and Radiation-Brazil (SCAR-B) field project took place in the Brazilian Amazon and cerrado regions in August-September 1995 as a collaboration between Brazilian and American scientists. SCAR-B, a comprehensive experiment to study biomass burning, emphasized measurements of surface biomass, fires, smoke aerosol and trace gases, clouds, and radiation. their climatic effects, and remote sensing from aircraft and satellites. It included aircraft and ground-based in situ measurements of smoke emission factors and the compositions, sizes, and optical properties of the smoke particles; studies of the formation of ozone; the transport and evolution of smoke; and smoke interactions with water vapor and clouds. This overview paper introduces SCAR-B and summarizes some of the main results obtained so far. (1) Fires: measurements of the size distribution of fires, using the 50 m resolution MODIS Airborne Simulator, show that most of the fires are small (e.g. 0.005 square km), but the satellite sensors (e.g., AVHRR and MODIS with I km resolution) can detect fires in Brazil which are responsible for 60-85% of the burned biomass: (2) Aerosol: smoke particles emitted from fires increase their radius by as much as 60%, during their first three days in the atmosphere due to condensation and coagulation, reaching a mass median radius of 0.13-0.17 microns: (3) Radiative forcing: estimates of the globally averaged direct radiative forcing due to smoke worldwide, based on the properties of smoke measured in SCAR-B (-O.l to -0.3 W m(exp -2)), are smaller than previously modeled due to a lower single-scattering albedo (0.8 to 0.9), smaller scattering efficiency (3 square meters g(exp -2) at 550 nm), and low humidification factor; and (4) Effect on clouds: a good relationship was found between cloud condensation nuclei and smoke volume concentrations, thus an increase in the smoke emission is expected to affect cloud properties. In SCAR-B, new techniques were developed for deriving the absorption and refractive index of smoke from ground-based remote sensing. Future spaceborne radiometers (e.g., MODIS on the Earth Observing System), simulated on aircraft, proved to be very useful for monitoring smoke properties, surface properties, and the impacts of smoke on radiation and climate.

Kaufman, Y. J.↗

Price Formation and Grid Operation Impacts from Variable Renewable Energy Resources

Increasing amounts of Variable Renewable Energy Resources (VREs) impact electricity markets and their operation. VREs are intermittent, zero marginal cost resources that tend to displace emissions-intensive generators in electricity dispatch, reducing emissions, but impacting price formation, revenue sufficiency, reliability, and market power mitigation processes of electricity markets. But VREs are not the only factor that affects operational and financial challenges in electricity markets. Declining natural gas prices, changing resource mixes, as well as different electricity market designs and regulatory policies all factor into the challenges both electricity market participants and operators face in today’s electricity markets. With this in-depth examination of electricity markets and related literature review, we aim to inform on key challenges of market design and operation for successful integration of large amounts of zero marginal cost resources. We’ve identified several areas, including VREs impact on price formation, revenue sufficiency, reliability, market power monitoring and mitigation, as well as how state-level incentives and market design impact VREs and these challenges. With each key challenge, we survey the literature to answer the question: To what extent is the problem, and how has it evolved over time? We first conduct a thorough review of ongoing challenges in electricity markets to understand the problem and review the empirical literature to capture important findings on how VREs, specifically, impact the problem. From this review, we highlight metrics that are important to understanding VRE integration and how market designs and outcomes are evolving with increasing levels of VREs. We propose several empirical models for future research to determine the impact of VREs on these identified challenges.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Programmed administration of parathyroid hormone increases bone formation and reduces bone loss in hindlimb-unloaded ovariectomized rats

Gonadal insufficiency and reduced mechanical usage are two important risk factors for osteoporosis. The beneficial effects of PTH therapy to reverse the estrogen deficiency-induced bone loss in the laboratory rat are well known, but the influence of mechanical usage in this response has not been established. In this study, the effects of programed administration of PTH on cancellous bone volume and turnover at the proximal tibial metaphysis were determined in hindlimb-unloaded, ovariectomized (OVX), 3-month-old Sprague-Dawley rats. PTH was administered to weight-bearing and hindlimb-unloaded OVX rats with osmotic pumps programed to deliver 20 microg human PTH (approximately 80 microg/kg x day) during a daily 1-h infusion for 7 days. Compared with sham-operated rats, OVX increased longitudinal and radial bone growth, increased indexes of cancellous bone turnover, and resulted in net resorption of cancellous bone. Hindlimb unloading of OVX rats decreased longitudinal and radial bone growth, decreased osteoblast number, increased osteoclast number, and resulted in a further decrease in cancellous bone volume compared with those in weight-bearing OVX rats. Programed administration of PTH had no effect on either radial or longitudinal bone growth in weight-bearing and hindlimb-unloaded OVX rats. PTH treatment had dramatic effects on selected cancellous bone measurements; PTH maintained cancellous bone volume in OVX weight-bearing rats and greatly reduced cancellous bone loss in OVX hindlimb-unloaded rats. In the latter animals, PTH treatment prevented the hindlimb unloading-induced reduction in trabecular thickness, but the hormone was ineffective in preventing either the increase in osteoclast number or the loss of trabecular plates. Importantly, PTH treatment increased the retention of a baseline flurochrome label, osteoblast number, and bone formation in the proximal tibial metaphysis regardless of the level of mechanical usage. These findings demonstrate that programed administration of PTH is effective in increasing osteoblast number and bone formation and has beneficial effects on bone volume in the absence of weight-bearing and gonadal hormones. We conclude that the actions of PTH on cancellous bone are independent of the level of mechanical usage.

NASA Discipline Musculoskeletal↗

Direct Catalytic Conversion of Ethanol to C 5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Abstract Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C 5+ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd‐promoted ZnO‐ZrO 2 catalyst. The sequence of reaction steps involved in the C 5+ ketone formation from ethanol was determined. The key reaction steps were found to be the in situ generation of the acetone intermediate and the cross‐aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd–Zn alloy in situ was identified to be the critical factor in maintaining high yield to the C 5+ ketones and the stability of the catalyst. A yield of >70 % to C 5+ ketones was achieved over a 0.1 % Pd‐ZnO‐ZrO 2 mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.

Subramaniam, Senthil↗

Polymer, Additives, and Processing Effects on N95 Filter Performance

The current severe acute respiratory syndrome coronavirus 2 (SARS-COV-2) pandemic has highlighted the need for personal protective equipment, specifically filtering facepiece respirators like N95 masks. While it is common knowledge that polypropylene (PP) is the industry standard material for filtration media, trial and error is often required to identify suitable commercial precursors for filtration media production. This work aims to identify differences between several commercial grades of PP and demonstrate the development of N95 filtration media with the intent that the industry partners can pivot and help address N95 shortages. Three commercial grades of high melt flow index PP were melt blown at Oak Ridge National Laboratory and broadly characterized by several methods including differential scanning calorimetry (DSC), X-ray diffraction (XRD), and neutron scattering. Despite the apparent similarities (high melt flow and isotacticity) between PP feedstocks, the application of corona charging and charge enhancing additives improve each material to widely varying degrees. From the analysis performed here, the most differentiating factor appears to be related to crystallization of the polymer and the resulting electret formation. Materials with higher crystallization onset temperatures, slower crystallization rates, and larger number of crystallites form a stronger electret and are more effective at filtration.

36 MATERIALS SCIENCE↗

Investigation of core transport changes in DIII-D discharges with off-axis T e profile peaks

Abstract DIII-D discharges that transition to H-mode solely with off-axis electron cyclotron heating (ECH) often exhibit strong off-axis peaking of electron temperature profiles at the heating location. Electron heat transport properties near these off-axis temperature peaks have been studied using modulated ECH. The Fourier analyzed electron temperature data have been used to infer electron thermal diffusivity. Comparisons with numerical solutions of the time-dependent electron thermal equation find that the data are consistent with a narrow region with electron diffusivity χ e an order of magnitude lower than the average value across the plasma, suggesting an electron internal transport barrier (ITB) near the ECH heating location. Detailed profile analysis and equilibrium reconstructions suggest that the formation of these ITBs are correlated with off-axis values of the safety factor q being near 1. Furthermore, the ECH driven H-mode discharges demonstrate more rapid electron heating rate near the ECH deposition location than L-mode discharges with higher auxiliary ECH heating power. Additional modeling attributes this difference to the modification of electron heat transport in the core at the L-H transition, which also sustains the off-axis electron temperature peaks.

Physics↗

Size-resolved Eddy-Covariance Particle Flux Measurement during the TRACER Campaign (Final Report)

The main goal of the TRacking Aerosol Convection interactions ExpeRiment (TRACER) campaign was to study aerosol–cloud interactions during deep convection over the Houston area. This project deployed a suite of instrumentation with the aim to (1) quantify turbulent vertical particle fluxes during at DOE-ARM sites, including TRACER, (2) assess hygroscopic growth factors and hygroscopicity parameters of the material driving modal aerosol growth during new particle formation and growth events, (3) derive turbulent aerosol mass fluxes using co-located Doppler LIDAR measurements, and (4) create quality-controlled PI data products to support future research utilizing data collected during the TRACER campaign. This report summarized the main findings from the deployments at two DOE-ARM sites. Briefly, we found that new particle formation may occur aloft, in a residual layer, near the top of the boundary layer. Small grown particles appear later due to downward mixing with daytime turbulence. The species that are responsible for aerosol modal growth had hygroscopicity parameters varying between 0.05 and 0.34. These values systematically depended on the wind sector, suggesting that the chemical composition of the precursors differed. This work demonstrated that lidar retrievals of the elastic backscatter and Doppler velocity can be used to obtain surface number emissions of particles with a diameter greater than 0.53 µm. During TRACER, emission particle number fluxes peaked near ∼ 100 cm−2 s−1. Multiple quality-controlled PI data products that will support future TRACER related science were generated and made publically available.

54 ENVIRONMENTAL SCIENCES↗

Variable Effects of Dispersed Nanoparticles on Triboelectric Nanogenerators

Technology has recently seen a drastic physical downsizing. Wearable and small devices with lower power demands have become the norm and continue to be more prominent in daily life. With modern devices growing smaller and requiring less electricity, a power source will always be needed. Contemporary batteries are the most common means to power small electronics. However, reliance on conventional batteries may prove insufficient due to the non renewable resources (Li, Ni, Co) required to power the growing number of individual devices each person may own. Additionally, the infrastructure required to harvest and recycle the sheer number of batteries produced presents a further logistic issue to be addressed. A promising alternative to batteries is the usage of triboelectric nanogenerators (TENGs). TENGs are a class of energy harvesting devices that utilize triboelectric generation to convert mechanical/kinetic energy into electrical energy and have exhibited efficiencies up to 85 % at low frequencies. TENGs exhibit a high voltage but low current. Even with the high voltage, the low current output proves to be a significant factor preventing undoped TENGs from being commercially viable. This review will investigate factors that increase the total current produced by TENGs when nanoparticles are utilized in TENGs. Factors such as increasing porosity, surface area, surface charge density, charge storage, deep trap formation, and dielectric constant can be altered to affect the total current by impregnating nanoparticles into the polymer material will be explored.

36 MATERIALS SCIENCE↗

Variable Effects of Dispersed Nanoparticles on Triboelectric Nanogenerators

Technology has recently seen a drastic physical downsizing. Wearable and small devices with lower power demands have become the norm and continue to be more prominent in daily life. With modern devices growing smaller and requiring less electricity, a power source will always be needed. Contemporary batteries are the most common means to power small electronics. However, reliance on conventional batteries may prove insufficient due to the non renewable resources (Li, Ni, Co) required to power the growing number of individual devices each person may own. Additionally, the infrastructure required to harvest and recycle the sheer number of batteries produced presents a further logistic issue to be addressed. A promising alternative to batteries is the usage of triboelectric nanogenerators (TENGs). TENGs are a class of energy harvesting devices that utilize triboelectric generation to convert mechanical/kinetic energy into electrical energy and have exhibited efficiencies up to 85 % at low frequencies. TENGs exhibit a high voltage but low current. Even with the high voltage, the low current output proves to be a significant factor preventing undoped TENGs from being commercially viable. This review will investigate factors that increase the total current produced by TENGs when nanoparticles are utilized in TENGs. Factors such as increasing porosity, surface area, surface charge density, charge storage, deep trap formation, and dielectric constant can be altered to affect the total current by impregnating nanoparticles into the polymer material will be explored.

42 ENGINEERING↗

On the synchronizability and detectability of random PPM sequences

The problem of synchronization and detection of random pulse-position-modulation (PPM) sequences is investigated under the assumption of perfect slot synchronization. Maximum-likelihood PPM symbol synchronization and receiver algorithms are derived that make decisions based both on soft as well as hard data; these algorithms are seen to be easily implementable. Bounds derived on the symbol error probability as well as the probability of false synchronization indicate the existence of a rather severe performance floor, which can easily be the limiting factor in the overall system performance. The performance floor is inherent in the PPM format and random data and becomes more serious as the PPM alphabet size Q is increased. A way to eliminate the performance floor is suggested by inserting special PPM symbols in the random data stream.

Georghiades, Costas N.↗

Molecular gas and star formation in HI-deficient Virgo cluster galaxies

Mapping of the CO emission line in 42 Virgo cluster galaxies reveals that the molecular gas contents and distributions are roughly normal in severaly HI-deficient Virgo spirals. The survival of the molecular component mitigates the impact of the HI-stripping on star formation and subsequent galactic evolution. For spirals which are deficient in HI by a factor of 10, far-infrared, H alpha line, and nonthermal radio continuum luminosities are lower by no more than a factor of 2. The fact that the inner galactic disks are stripped of HI, while CO is normal, suggests that the lifetime of the molecular phase is approximately one billion years in the inner regions of luminous spirals.

Kenney, Jeffrey D.↗

On the synchronizability and detectability of random PPM sequences

The problem of synchronization and detection of random pulse-position-modulation (PPM) sequences is investigated under the assumption of perfect slot synchronization. Maximum likelihood PPM symbol synchronization and receiver algorithms are derived that make decisions based both on soft as well as hard data; these algorithms are seen to be easily implementable. Bounds were derived on the symbol error probability as well as the probability of false synchronization that indicate the existence of a rather severe performance floor, which can easily be the limiting factor in the overall system performance. The performance floor is inherent in the PPM format and random data and becomes more serious as the PPM alphabet size Q is increased. A way to eliminate the performance floor is suggested by inserting special PPM symbols in the random data stream.

Georghiades, Costas N.↗

Integration of altitude and airspeed information into a primary flight display via moving-tape formats: Evaluation during random tracking task

A ground-based aircraft simulation study was conducted to determine the effects on pilot preference and performance of integrating airspeed and altitude information into an advanced electronic primary flight display via moving-tape (linear moving scale) formats. Several key issues relating to the implementation of moving-tape formats were examined in this study: tape centering, tape orientation, and trend information. The factor of centering refers to whether the tape was centered about the actual airspeed or altitude or about some other defined reference value. Tape orientation refers to whether the represented values are arranged in descending or ascending order. Two pilots participated in this study, with each performing 32 runs along seemingly random, previously unknown flight profiles. The data taken, analyzed, and presented consisted of path performance parameters, pilot-control inputs, and electrical brain response measurements.

Abbott, Terence S.↗