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At least 811 records · Page 45

Atmospheric Transformation of Refrigerants: Current Research Developments and Knowledge Gaps

Refrigerants have evolved through the years to reduce their global warming potential while providing sufficient cooling in refrigeration systems. Replacements for hydrofluorocarbons (HFCs) and chlorofluorocarbons (CFCs) are the hydrofluoroolefins (HFOs), which contain reactive double bonds that decrease the atmospheric lifetime of fluorinated compounds. However, the transformation of unsaturated fluorinated compounds in the atmosphere could generate persistent pollutants, particularly trifluoroacetic acid (TFA) which is the simplest Perfluoroalkyl carboxylic acids (PFCAs). Understanding the transformation of refrigerants is critical in assessing their contribution to atmospheric levels of TFA and their impact on watersheds and human health. This article will present the reactivity of the refrigerants, atmospheric oxidation source, and sink processes of fluorinated refrigerants under daytime conditions, particularly the variability of TFA from refrigerants. Moreover, the discussion will suggest experimental procedures that can quantify the low concentration (~parts per trillion) of TFA generated from the transformation of HFOs. New state-of-the-art techniques such as chemical ionization mass spectrometers (HR-CIMS) will be assessed in providing high temporal resolution (minutes to hourly) to fully capture the atmospheric sources and variability of TFA. Likewise, local, regional, and global concentrations of TFA accounted from the oxidation of refrigerants will be examined. This will include data from both experimental procedures and simulation models. Participation of TFA in critical atmospheric processes such as new particle formation will also be included in this study. Lastly, overall knowledge gaps related to the oxidation products and their dispersion in the environment will be summarized to guide future research needs.

Salvador, Christian↗

Solidification of hypermonotectic Al-In alloys under microgravity conditions

Four samples of the Al-In system having monotectic and hypermonotectic compositions that were solidified under microgravity during the NASA-SPAR IX flight of January 20, 1981, are considered. The experimental thermal and physicochemical conditions that were actually achieved are analyzed. Radiographic and metallographic observations of the samples reveal a nonregular dispersed primary phase inside the monotectic matrix. These observations are discussed in relation to capillarity and solidification aspects. A key finding is the preservation of a certain degree of dispersion of the indium primary phase. This result differs fundamentally from the results obtained under microgravity conditions on the same system and compositions (Gelles and Markworth, 1980; Alborn and Loehberg, 1979). The results are seen as clearly establishing that the space environment can be used to obtain dispersed structures from hypermonotectic alloys.

Potard, C.↗

Kinematics of the ion tail of comet P/Swift-Tuttle

We have obtained long-slit high resolution spectra of the H2O(+) 6199 A complex in the near tail of comet P/Swift-Tuttle. The observations were made using the Hamilton echelle spectrometer fed by the Lick Observatory 0.6 m coude auxiliary telescope. For most of our observations, the spectral slit was aligned along the Sun-tail axis and the cometary nucleus was placed at one end of the slit, giving us spectra having the spatial and spectral resolution needed to measure the radial velocity and velocity dispersion continuously down the cometary tail out to a distance of 4X10(exp 5) km. The radial velocities confirm the earlier more restricted observations by Rauer & Jockers (1993) and by Wyckoff & Lindholm (1994) showing that the tail motions are indeed bulk flows in the antisolar direction. Out to 3X10(exp 5) km in the tail typical bulk flows are at a speed of approximately 30 km/s. The velocity dispersion, (sigma(sub r)), of the H2O(+) lines follows a pattern that is quite systematic; sigma(sub r) is smallest near the cometary nucleus, and steadily increases down the tail. The highest velocity dispersions are found ahead of the nucleus and off the tail axis. These velocity dispersions are equivalent to ion temperatures ranging from 10(exp 5) to 10(exp 6) K. We note a clear anticorrelation between the H2O(+) line intensities (related to the ion density) and the bulk flow and dispersion velocities; direct mass loading of the solar wind by the observed water ions may be responsible. We discuss several approximate equipartition methods used to infer local magnetic fields induced by the interaction of the cometary ions with the solar wind particle/field stream. Typical fields derived are near 50 nT. The measured tailward accelerations are consistent with this order of magnitude B field.

Spinrad, Hyron↗

Spectroscopic Characterization of redMaPPer Galaxy Clusters with DESI

Optical galaxy cluster identification algorithms such as redMaPPer promise to enable an array of astrophysical and cosmological studies, but suffer from biases whereby galaxies in front of and behind a galaxy cluster are mistakenly associated with the primary cluster halo. These projection effects caused by irreducible photometric redshift uncertainty must be quantified to facilitate the use of optical cluster catalogues. We present measurements of galaxy cluster projection effects and velocity dispersion using spectroscopy from the Dark Energy Spectroscopic Instrument. Our findings are as follows: we confirm that the fraction of redMaPPer putative member galaxies mistakenly associated with cluster haloes is richness dependent, being more than twice as large at low richness than high richness; we present the first spectroscopic evidence of an increase in projection effects with increasing redshift, by as much as 25 per cent from $z\sim 0.1$ to $z\sim 0.2$; moreover, we find qualitative evidence for luminosity dependence in projection effects, with fainter galaxies being more commonly far behind clusters than their bright counterparts; finally, we fit the scaling relation between measured mean spectroscopic richness and velocity dispersion, finding an implied linear scaling between spectroscopic richness and halo mass. We discuss further directions for the application of spectroscopic data sets to improve use of optically selected clusters to test cosmological models.

clusters↗

Three-dimensional dispersion in the type-II Dirac semimetals PtTe 2 and PdTe 2 revealed through circular dichroism in angle-resolved photoemission spectroscopy

PtTe 2 and PdTe 2 are among the first transition metal dichalcogenides that were predicted to host type-II Dirac fermions, exotic particles prohibited in free space. These materials are layered and air stable, which makes them top candidates for technological applications that take advantage of their anisotropic magnetotransport properties. Here, in this work, we provide a detailed characterization of the electronic structure of PtTe 2 and PdTe 2 using angle-resolved photoemission spectroscopy (ARPES) and density functional theory calculations, offering an alternative interpretation for one of the Dirac-like dispersions in these materials. Through the use of circularly polarized light, we report a different behavior of such dispersion in PdTe 2 compared to PtTe 2 , that we relate to a symmetry analysis of the dipole matrix element. Such analysis reveals a link between the observed circular dichroism and the different momentum-dependent terms in the dispersion of these two compounds, despite their close similarity in crystal structure. Additionally, our data show a clear difference in the circular dichroic signal for the type-II Dirac cones characteristic of these materials, compared to their topologically protected surface states. Our paper provides a useful reference for the ARPES characterization of other transition metal dichalcogenides with topological properties and illustrates the use of circular dichroism as a guide to identify the topological character and attributes of two otherwise equivalent band dispersions.

angle-resolved photoemission spectroscopy↗

Using Machine Learning to Predict Cloud Turbulent Entrainment–Mixing Processes

Different turbulent entrainment–mixing mechanisms between clouds and environment are essential to cloud–related processes; however, accurate representation of entrainment–mixing in weather/climate models still poses a challenge. This study exploits the use of machine learning (ML) to address this challenge. Four ML (Light Gradient Boosting Machine [LGB], eXtreme Gradient Boosting, Random Forest, and Support Vector Regression) are examined and compared. It is found that LGB performs best, and thus is selected to understand the impact of entrainment–mixing on microphysics using simulation data from Explicit Mixing Parcel Model. Compared with traditional parameterizations, the trained LGB provides more accurate microphysical properties (number concentration and cloud droplet spectral dispersion). The partial dependences of predicted microphysics on features exhibit a strong alignment with physical mechanisms and expectations, as determined by the interpreting method, thus overcoming the limitations of the “black box” scheme. The underlying mechanisms are that the smaller number concentration and larger spectral dispersion correspond to more inhomogeneous entrainment–mixing. Specifically, number concentration after entrainment–mixing is positively correlated with adiabatic number concentration and liquid water content affected by entrainment–mixing, and inversely correlated with adiabatic volume mean radius. Spectral dispersion after entrainment–mixing is negatively correlated with liquid water content affected by entrainment–mixing, turbulent dissipation rate and relative humidity of entrained air. Sensitivity analysis further suggests that number concentration is mainly determined by cloud microphysical properties whereas spectral dispersion is influenced by both cloud microphysical properties and environmental variables. The results indicate that the LGB scheme has the potential to enhance the representation of entrainment–mixing in weather/climate models.

54 ENVIRONMENTAL SCIENCES↗

Hydrogen bonds and dispersion forces serving as molecular locks for tailored Group 11 bis(amidine) complexes

A flexible polydentate bis(amidine) ligand LH 2 , LH 2 = {CH 2 NH( t Bu)C=N-2-(6-MePy)} 2 , operates as a molecular lock for various coinage metal fragments and forms the dinuclear complexes [LH 2 (MCl) 2 ], M = Cu (1), Au (2), the coordination polymer [{(LH 2 ) 2 (py) 2 (AgCl) 3 }(py) 3 ] n (3), and the dimesityl-digold complex [LH 2 (AuMes) 2 ] (4) by formal insertion of MR fragments (M = Cu, Ag, Au; R = Cl, Mes) into the N–H∙∙∙N hydrogen bonds of LH 2 in yields of 43–95%. Complexes 1, 2, and 4 adopt C 2 -symmetrical structures in the solid state featuring two interconnected 11-membered rings that are locked by two intramolecular N–H∙∙∙R–M hydrogen bonds. QTAIM analyses of the computational geometry-optimized structures 1a, 2a, and 4a reveal 13, 11, and 22 additional bond critical points, respectively, all of which are related to weak intramolecular attractive interactions, predominantly representing dispersion forces, contributing to the conformational stabilization of the C2-symmetrical stereoisomers in the solid state. Variable-temperature 1 H NMR spectroscopy in combination with DFT calculations indicate a dynamic conformational interconversion between two C 2 -symmetrical ground state structures in solution (ΔG ‡ c = 11.1–13.8 kcal mol –1 ), which is accompanied by the formation of an intermediate possessing C i symmetry that retains the hydrogen bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dust extinction and molecular gas in the dark cloud IC 5146

In this paper we describe a powerful method for mapping the distribution of dust through a molecular cloud using data obtained in large-scale, multiwavelength, infrared imaging surveys. This method combines direct measurements of near-infrared color excess and certain techniques of star counting to derive mean extinctions and map the dust column density distribution through a cloud at higher angular resolutions and greater optical depths than those achieved previously by optical star counting. We report the initial results of the application of this method to a dark cloud complex near the cluster IC 5146, where we have performed coordinated, near-infrared, JHK imaging and (13)CO, C(18)O, and CS millimeter-wave, molecular-line surveys of a large portion of the complex. More than 4000 stars were detected in our JHK survey of the cloud. Of these, all but about a dozen appear to be field stars not associated with the cloud. Star count maps at J band show a striking and detailed anticorrelation between the surface density of J-band sources and CO and CS molecular-line emission. We used the (H-K) colors and positions of nearly 1300 sources to directly measure and map the extinction and thus trace the dust column density through the cloud at an effective angular resolution of 1 min .5. We report an interesting correlation between the measured dispersion in our extinction determinations and the extinction. Modeling this relation indicates that effects of small-scale cloud structure dominate the uncertainties in our measurements. Moreover, we demonstrate that such observations can be used to place constraints on the nature of the spatial distribution of extinction on scales smaller than our resolution. In particular, we show that models in which the dust is distributed uniformly or in discrete high-extinction clumps on scales smaller than (1 min .5) are inconsistent with the observations. We have derived extinctions at the same positions and at the same angular resolution (1 min .7) as our molecular-line observations. This enabled a direct comparison of (13)CO, C(18)O, and CS integrated intensities and column densities with A(sub V) for more than 500 positions in the cloud, corresponding to a range in A(sub V) between 0 to 32 mag of extinction. We found the integrated intensities of (13)CO, C(18)O, and CS to be roughly linearly correlated with extinction over different ranges of extinction. However, for all three molecules we find the scatter in the observed relations to be larger than can be accounted for by instrumental error, suggesting that there are large intrinsic variations in the abundances or excitation of the molecules through the cloud. Mean abundances for all the molecules relative to hydrogen were directly derived from the data. The ratio of (13)CO to C(18)O abundances was found to be significantly higher than the terrestrial ratio in regions where extinction is less than 10 mag. In the same region, the dispersion in the abundance ratio is also found to be very large, suggesting that the abundances of one or both molecules are very unstable even at relatively large cloud optical depths. Beyond 10 mag of extinction the abundances of both species appear very stable with their ratio close to the terrestrial value.

Lada, Charles J.↗

Cation Migration and LSCF/SDC Decomposition Related to Long-Term Operation Mode as Revealed by Electron Microscopy

This study utilized energy dispersive spectroscopy (EDS) in a scanning electron microscope (SEM) and a scanning transmission electron microscope (STEM) in order to track cation migration and related particle decomposition for air electrode components of solid oxide cells. The influence of a Sm-doped ceria (SDC) barrier layers was assessed for three operation modes (fuel cell, electrolysis, reversible) over long time periods (1000-1500 hours). Composition profiles across air electrode/electrolyte interfaces indicated negligible accumulation of La/Sr cations to the yttria-stabilized zirconia (YSZ) electrolyte during operation. Instead, air electrode particles composed of SDC and/or La-Sr-Co-Fe-oxides (LSCF) exhibited decomposition by Sr evaporation and Sm migration to LSCF particle edges.

Picard, Yoosuf↗

Restoration of weak localization in bilayer graphene by a molecular thin film

Quantum coherent effects can be probed in multilayer graphene through electronic transport measurements at low temperatures. In particular, bilayer graphene (BLG) is known to be susceptible to quantum interference corrections of the conductivity, presenting weak localization at all electronic densities, and dependent on different scattering mechanisms such as those related to the trigonal warping of the electron dispersion near the K and K′ valleys. Proximity effects with a molecular thin film influence these scattering mechanisms, which can be quantified through the known theory of magnetoconductance for BLG. Here, we present electronic transport measurements in a copper-phthalocyanine (CuPc) / BLG / hexagonal boron nitride (h-BN) heterostructure that suggest the restoration of weak localization in BLG, associated to a reduction of trigonal warping effects, that are known to suppress weak localization in BLG. Additionally, we observe a charge transfer of 3.6×10 12 cm −2 from the BLG to the molecules, as well as a very small degradation of the mobility of the BLG/h-BN heterostructure upon the deposition of CuPc. The molecular arrangement of the CuPc thin film is characterized in a control sample through transmission electron microscopy, that we relate to the electronic transport results.

bilayer graphene↗

BayoTech Risk and Modeling Support of NM Gas Site

The BayoTech hydrogen generation system has been evaluated in terms of safety considerations at the NM Gas site. The consequence of a leak in different components in the system was evaluated in terms of plume dispersion and overpressure. Additionally, the likelihood of a leak scenario for different hydrogen components was identified. The worst-case plume dispersion cases, full-bore leaks, resulted in relatively large plumes. However, these cases were noted to be far less likely than the partial break cases that were evaluated. The partial break cases resulted in nearly negligible plume lengths. Similarly, the overpressure analysis of the full-bore break scenarios resulted in much larger overpressures than the partial break cases (which resulted in negligible overpressure at the lot line). There were several cases evaluated in the analysis that represented leak scenarios from both hydrogen and natural gas sources. Generally, the natural gas leak scenarios resulted in a smaller horizontal impact than that of hydrogen leaks. The worst-case consequence from a hydrogen leak resulted from the compressors, storage pods, or dispensing system. To consider the safety features that may isolate the leak, the consequence was evaluated at different times after the leak event to show the reduction of pressure. After 2 seconds, the plume dispersion from this event is contained within the perimeter of the site. The worst-case consequences show that the plume may disperse to adjacent facilities and to the street. When considering both likelihood and consequence, the risk may be considered low because the maximum frequency of a full-bore leak from any component within the hydrogen compound is 8.2 E-5/yr. This means that a full-bore leak is expected to occur less than once every 10,000 years. The risk can be further reduced by implementing mitigative countermeasures, such as CMU walls along the sides of the equipment compound. This would reduce the overall consequence of the worst-case dispersion scenarios (horizontal impact of plume). In terms of siting and safety analysis, the NFPA 2 code was used to provide a high-level evaluation of the current site plan. The most limiting equipment in terms of set-back distance are the compressors/storage units because of the high-pressure hydrogen. The site layout was evaluated for an acceptable location for the compression/storage unit based on NFPA 2 set-back distances. It is important to note that the NFPA 2 set-back distances consider both likelihood and consequence. This is important because the worst-case results evaluated herein also represent the least likely leak scenario. Other site-specific considerations were evaluated, including the parking shade structure with photovoltaic cells and refueling vehicles. These issues were dispositioned and determined to not present a safety risk.

08 HYDROGEN↗

Fast radio burst dispersion measure distribution as a probe of helium reionization

Fast radio burst (FRB) discoveries are occurring rapidly, with thousands expected from upcoming surveys. The dispersion measures (DM) observed for FRB include important information on cosmological distances and the ionization state of the universe from the redshift of emission until today. Rather than considering the DM–redshift relation, we investigate the statistical ensemble of the distribution of dispersion measures. Here, we explore the use of this abundance information, with and without redshift information, to probe helium reionization through simulated data to redshift z = 6. Carrying out Monte Carlo simulations of FRB survey samples, we examine the effect of different source redshift distributions, host galaxy models, sudden vs gradual reionization, and covariance with cosmological parameters on determination of helium reionization properties. We find that a fluence limited survey with 10 4 FRBs can discriminate different helium reionization histories at ~6σ using the DM-distribution of bursts, without redshift information (and ~10σ with redshifts).

79 ASTRONOMY AND ASTROPHYSICS↗

Particle Distribution in Suspension Shear Flow

An earlier proposed constitutive relation for normal stresses originated by random particle fluctuations is used to describe a joint effect of thermal and shear-induced fluctuations on concentrational distributions in suspension flow. Averaged products of components of the fluctuation velocity are evaluated on a basis of the rational mechanics approach combined with a simple kinematic consideration. The equation of momentum conservation of the dispersed phase of a suspension closed with this constitutive relation is applied to unidirectional shear flow in the gravity field and to rotational Couette flow. Coupling of the thermal and shear-induced fluctuations results in that the ability of shear flow to suspend particles has a minimum at a certain particle size, all other things being equal. The developed model provides also for a reasonable explanation of particle distributions observed in Couette flow. The approach based on the consideration of momentum balance for the dispersed phase is proved to lead to an effective equation of convective diffusion of the suspended particles. Coefficients of mutual diffusion due to both thermal and shear-induced fluctuations are drastically different from corresponding self-diffusivities as regards both their scaling and their concentrational dependence.

Buyevich, Yu A.↗

Performance of a Compression-ignition Engine with a Precombustion Chamber Having High-Velocity Air Flow

Presented here are the results of performance tests made with a single-cylinder, four stroke cycle, compression-ignition engine. These tests were made on a precombustion chamber type of cylinder head designed to have air velocity and tangential air flow in both the chamber and cylinder. The performance was investigated for variable load and engine speed, type of fuel spray, valve opening pressure, injection period and, for the spherical chamber, position of the injection spray relative to the air flow. The pressure variations between the pear-shaped precombustion chamber and the cylinder for motoring and full load conditions were determined with a Farnboro electric indicator. The combustion chamber designs tested gave good mixing of a single compact fuel spray with the air, but did not control the ensuing combustion sufficiently. Relative to each other, the velocity of air flow was too high, the spray dispersion by injection too great, and the metering effect of the cylinder head passage insufficient. The correct relation of these factors is of the utmost importance for engine performance.

Spanogle, J A↗

Evidence for dispersing 1D Majorana channels in an iron-based superconductor

The possible realization of Majorana fermions as quasiparticle excitations in condensed-matter physics has created much excitement. Most studies have focused on Majorana bound states; however, propagating Majorana states with linear dispersion have also been predicted. Here, we report scanning tunneling spectroscopic measurements of crystalline domain walls (DWs) in FeSe 0.45 Te 0.55 . We located DWs across which the lattice structure shifts by half a unit cell. These DWs have a finite, flat density of states inside the superconducting gap, which is a hallmark of linearly dispersing modes in one dimension. This signature is absent in DWs in the related superconductor, FeSe, which is not in the topological phase. Our joint data are consistent with the observation of dispersing Majorana states at a π-phase shift DW in a proximitized topological material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On Lateral Viscosity Contrast in the Mantle and the Rheology of Low-Frequency Geodynamics

Mantle-wide heterogeneity is largely controlled by deeply penetrating thermal convective currents. These thermal currents are likely to produce significant lateral variation in rheology, and this can profoundly influence overall material behaviour. How thermally related lateral viscosity variations impact models of glacio-isostatic and tidal deformation is largely unknown. An important step towards model improvement is to quantify, or bound, the actual viscosity variations that characterize the mantle. Simple scaling of viscosity to shear-wave velocity fluctuations yields map-views of long- wavelength viscosity variation. These give a general quantitative description and aid in estimating the depth dependence of rheological heterogeneity throughout the mantle. The upper mantle is probably characterized by two to four orders of magnitude variation (peak-to-peak). Discrepant time-scales for rebounding Holocene shorelines of Hudson Bay and southern Iceland are consistent with this characterization. Results are given in terms of a local average viscosity ratio, (Delta)eta(bar)(sub i), of volumetric concentration, phi(sub i). For the upper mantle deeper than 340 km the following reasonable limits are estimated for (delta)eta(bar) approx. equal 10(exp -2): 0.01 less than or equal to phi less than or equal to 0.15. A spectrum of ratios (Delta)eta(bar)(sub i) less than 0.1 at concentration level eta(sub i) approx. equal 10(exp -6) - 10(exp -1) in the lower mantle implies a spectrum of shorter time-scale deformational response modes for second-degree spherical harmonic deformations of the Earth. Although highly uncertain, this spectrum of spatial variation allows a purely Maxwellian viscoelastic rheology simultaneously to explain all solid tidal dispersion phenomena and long-term rebound-related mantle viscosity. Composite theory of multiphase viscoelastic media is used to demonstrate this effect.

Ivins, Erik R.↗

Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts

Abstract Atomically dispersed and nitrogen coordinated single metal sites (M‐N‐C, M=Fe, Co, Ni, Mn) are the popular platinum group‐metal (PGM)‐free catalysts for many electrochemical reactions. Traditional wet‐chemistry catalyst synthesis often requires complex procedures with unsatisfied reproducibility and scalability. Here, we report a facile chemical vapor deposition (CVD) strategy to synthesize the promising M‐N‐C catalysts. The deposition of gaseous 2‐methylimidazole onto M‐doped ZnO substrates, followed by an in situ thermal activation, effectively generated single metal sites well dispersed into porous carbon. In particular, an optimal CVD‐derived Fe‐N‐C catalyst exclusively contains atomically dispersed FeN 4 sites with increased Fe loading relative to other catalysts from wet‐chemistry synthesis. The catalyst exhibited outstanding oxygen‐reduction activity in acidic electrolytes, which was further studied in proton‐exchange membrane fuel cells with encouraging performance.

Liu, Shengwen↗

Importance of residence-time control of industrial screw-conveying reactors: Application to dilute-acid hydrolysis of biomass

Horizontal screw reactors are utilized in biorefineries for acid-catalyzed hydrolysis of xylan, which is a multi-step chemical reaction requiring accurate residence-time control. However, it is difficult to obtain online analytical measurement of reactant species. In this work, a residence-time distribution (RTD) is exhibited whose characteristics influence species yields. Sensitivity of product yield to RTD was investigated to understand the relative importance of operating control vs. inherent reactor dispersion. We find that reactor operation using a commonly used theoretical residence-time relationship can result in substantial yield losses. Instead, a model that accounts for the actual reactor RTD provides much improved results. The dispersion caused by reactor conditions only slightly hinders achieving theoretical optimal xylose yield (less than 3% yield loss for coefficient of variation less than 0.35), provided a validated RTD model is used to target the desired mean residence-time. In contrast, neglecting to account for the RTD by using the simplistic theoretical calculation results in xylose yields that are as much as 16% lower than the theoretical maximum.

09 BIOMASS FUELS↗