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At least 1,765 records · Page 98

A critical analysis of the accuracy of several numerical techniques for combustion kinetic rate equations

A detailed analysis of the accuracy of several techniques recently developed for integrating stiff ordinary differential equations is presented. The techniques include two general-purpose codes EPISODE and LSODE developed for an arbitrary system of ordinary differential equations, and three specialized codes CHEMEQ, CREK1D, and GCKP4 developed specifically to solve chemical kinetic rate equations. The accuracy study is made by application of these codes to two practical combustion kinetics problems. Both problems describe adiabatic, homogeneous, gas-phase chemical reactions at constant pressure, and include all three combustion regimes: induction, heat release, and equilibration. To illustrate the error variation in the different combustion regimes the species are divided into three types (reactants, intermediates, and products), and error versus time plots are presented for each species type and the temperature. These plots show that CHEMEQ is the most accurate code during induction and early heat release. During late heat release and equilibration, however, the other codes are more accurate. A single global quantity, a mean integrated root-mean-square error, that measures the average error incurred in solving the complete problem is used to compare the accuracy of the codes. Among the codes examined, LSODE is the most accurate for solving chemical kinetics problems. It is also the most efficient code, in the sense that it requires the least computational work to attain a specified accuracy level. An important finding is that use of the algebraic enthalpy conservation equation to compute the temperature can be more accurate and efficient than integrating the temperature differential equation.

Radhadrishnan, Krishnan↗

Microencapsulated PCM slurries for heat transfer and energy storage in spacecraft systems

The technical feasibility for providing significantly enhanced heat transport and storage as well as improved thermal control has been investigated during several Small Business Innovative Research (SBIR) programs for NASA, the United States Air Force (USAF), and the Strategic Defense Initiative Organization (SDIO) using microencapsulated phase change materials (PCMs) in both aqueous and nonaqueous two-component slurries. In the program for SDIO, novel two-component coolant fluids were prepared and successfully tested at both low (300 K) and intermediate temperatures (460 to 700 K). The two-component fluid slurries of microencapsulated PCMs included organic particles in aqueous and nonaqueous liquids, as well as microencapsulated metals that potentially could be carried by liquid metals or used as powdered heat sinks. Simulation and experimental studies showed that such active cooling systems could be designed and operated with enhancements of heat capacity that exceeded 10 times or 1000 percent that for the base fluid along with significant enhancement in the fluid's heat capacity. Furthermore, this enhancement provided essentially isothermal conditions throughout the pumped primary coolant fluid loop. The results suggest that together with much higher fluid thermal capacity, greater uniformity of temperature is achievable with such fluids, and that significant reductions in pumping power, system size, and system mass are also possible.

Colvin, David P.↗

Upper Temperature Limit of Environmental Barrier Coatings Based on Mullite and BSAS

Current state-of-the-art environmental barrier coatings (EBCs) for Si-based ceramics consist of three layers: a silicon bond coat, an intermediate mullite (3Al2O3-2SiO2) or mullite + BSAS (1-xBaO-xSrO-Al2O3-2SiO2) layer, and a BSAS top coat. Areas of concern for long-term durability are environmental durability, chemical compatibility, silica volatility, phase stability, and thermal conductivity. Variants of this family of EBCs were applied to monolithic SiC and melt infiltrated SiC/SiC composites. Reaction between BSAS and silica results in low melting (approx. 1300 C) glasses at T > 1400 C, which can cause the spallation of the EBC. At temperatures greater than 1400 C, the BSAS top coat also degrades by formation of a porous structure, and it suffers significant recession via silica volatilization in water vapor-containing atmospheres. All of these degradation mechanisms can be EBC life-limiting factors. BSAS undergoes a very sluggish phase transformation (hexagonal celsian to monoclinic celsian), the implications of which are not fully understood at this point. There was evidence of rapid sintering at temperatures as low as 1300 C, as inferred from the sharp increase in thermal conductivity.

Lee, Kang N.↗

The Asymmetric Inner Disk of the Herbig Ae Star HD 163296 in the Eyes of VLTI/MATISSE: Evidence for a Vortex?

Context.A complex environment exists in the inner few astronomical units of planet-forming disks. High-angular-resolution observa-tions play a key role in our understanding of the disk structure and the dynamical processes at work.Aims.In this study we aim to characterize the mid-infrared brightness distribution of the inner disk of the young intermediate-massstar HD 163296 from early VLTI/MATISSE observations taken in theL- andN-bands. We put special emphasis on the detection ofpotential disk asymmetries.Methods.We use simple geometric models to fit the interferometric visibilities and closure phases. Our models include a smoothedring, a flat disk with an inner cavity, and a 2D Gaussian. The models can account for disk inclination and for azimuthal asymmetriesas well. We also perform numerical hydrodynamical simulations of the inner edge of the disk.Results.Our modeling reveals a significant brightness asymmetry in theL-band disk emission. The brightness maximum of the asym-metry is located at the NW part of the disk image, nearly at the position angle of the semimajor axis. The surface brightness ratio inthe azimuthal variation is3.5±0.2. Comparing our result on the location of the asymmetry with other interferometric measurements,we confirm that the morphology of ther<0.3au disk region is time-variable. We propose that this asymmetric structure, located in ornear the inner rim of the dusty disk, orbits the star. To find the physical origin of the asymmetry, we tested a hypothesis where a vortexis created by Rossby wave instability, and we find that a unique large-scale vortex may be compatible with our data. The half-lightradius of theL-band-emitting region is0.33±0.01au, the inclination is52◦+5◦−7◦, and the position angle is143◦±3◦. Our models predictthat a non-negligible fraction of theL-band disk emission originates inside the dust sublimation radius forμm-sized grains. Refractorygrains or large (&10μm-sized) grains could be the origin of this emission.N-band observations may also support a lack of smallsilicate grains in the innermost disk (r.0.6au), in agreement with our findings fromL-band data.

J Varga↗

Development of a novel fcc structure for an amorphous-nanocrystalline Ti-33Nb-4Mn (at.%) ternary alloy

Highlights: • An amorphized-nanocrystalline TiNbMn alloy was obtained via mechanical alloying. • The obtained TiNbMn ternary alloy evolved with the mechanical alloying time. • At lower milling time, two nanocrystalline phases (bcc and fcc) were developed. • At higher milling time, a stable amorphous-nanocrystalline fcc-alloy was obtained. • The fcc structure has not been previously published for Ti based alloys. - Abstract: In this work, a novel amorphous-nanocrystalline titanium‑niobium‑manganese solid solution ternary alloy with a Ti-33Nb-4Mn (at.%) nominal composition was developed by a High-Energy Mechanical Alloying. Nb and Mn were added to the elemental Ti as a β-phase (bcc) stabilizer and an amorphization promoter, respectively. The system evolved from the elemental Ti, Nb and Mn raw materials to a body centred cubic (bcc) TiNbMn alloy and, finally, to the formation of an original and stable face centred cubic (fcc) nanocrystalline TiNbMn alloy, not reported until now, at short milling time (20 h). This alloy remains invariant until 120 h. In turn, the partial amorphization of the system occurs and increases until at intermediate milling time (80 h). The production of both original fcc and the amorphous TiNbMn alloy may be beneficial for reducing the Young's modulus and improving the mechanical strength pursued for the Ti alloy. The optimal milling time respect to the amorphization, nanocrystalline size and Fe mount from milling media was 60 h and 80 h (TiNbMn60h and TiNbMn80h), with > 50 wt% of an amorphous phase and a crystalline domain size of approximately 5 nm.

36 MATERIALS SCIENCE↗

Quantum spin liquid with emergent chiral order in the triangular-lattice Hubbard model

The interplay between spin frustration and charge fluctuation gives rise to an exotic quantum state in the intermediate-interaction regime of the half-filled triangular-lattice Hubbard model, while the nature of the state is under debate. Using the density matrix renormalization group with SU(2) spin ⓍU(1) charge symmetries implemented, we study the triangular-lattice Hubbard model defined on the long cylinder geometry up to circumference W=6. A gapped quantum spin liquid, with on-site interaction 9≲U/t≲10.75, is identified between the metallic and the antiferromagnetic Mott insulating phases. In particular, we find that this spin liquid develops a robust long-range spin scalar-chiral correlation as the system length L increases, which unambiguously unveils the spontaneous time-reversal symmetry breaking. In addition, the degeneracy of the entanglement spectrum supports symmetry fractionalization and spinon edge modes in the obtained ground state. The possible origin of chiral order in this intermediate spin liquid and its relation to the rotonlike excitations have also been discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Carbocation Stability in H-ZSM5 at High Temperature

Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 °C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and Tkatchenko-Scheffler van der Waals corrections. The embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tertbutyl cations exhibit significant populations (>10%). Moreover, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are possible at high temperatures relevant to some industrial uses of zeolite catalysts, although as the minority species in most cases.

36 MATERIALS SCIENCE↗

Nanoscale magnetic phase competition throughout the Ni 50– x Co x Mn 40 Sn 10 phase diagram: Insights from small-angle neutron scattering

The Ni 2 MnSn-derived Ni 50– x Co x Mn 25+ y Sn 25– y alloys are premier examples of a class of off-stoichiometric Heusler alloys recently discovered to exhibit attractive magnetic properties in tandem with extraordinarily reversible martensitic phase transformations. Multiferroicity, magnetic phase competition and separation, field-induced martensitic transformations, magnetic shape memory behavior, and sizable magneto-, elasto-, and barocaloric effects result, generating substantial interest and application potential. In this work we expand on a prior small-angle neutron scattering (SANS) study at a single composition (Ni 44 Co 6 Mn 40 Sn 10 ) by exploring all three main regions of the recently established Ni 50–x Co x Mn 40 Sn 10 phase diagram, i.e., at the representative y = 15 composition. Wide temperature and scattering wave-vector range (20–500K, 0.004–0.2Å –1 ) SANS data on x = 2, 6, and 14 polycrystals provide a detailed picture of the evolution in magnetic order and inhomogeneity. Consistent with recent studies with a variety of techniques, phase separation into short-range coexisting ferromagnetic and antiferromagnetic regions is deduced below the martensitic transformation at x = 2 and 6, with average ferromagnetic cluster spacing of ~13 nm. Remarkably, at x = 14, where the martensitic transformation is suppressed and ferromagnetic austenite is stabilized to low temperatures, nanoscopic magnetic inhomogeneity nevertheless persists. Further, distinct ferromagnetic clusters (~36-nm average spacing) in a ferromagnetic matrix are observed at intermediate temperatures, homogenizing into a uniform long-range ordered ferromagnet only at low temperatures. This unusual ferromagnet cluster/ferromagnet matrix inhomogeneity, as well as x -dependent subtleties of the superparamagnetic freezing of ferromagnetic clusters, are discussed in light of 55 Mn nuclear magnetic resonance data, and the recent observation of annealing-induced core/shell nanoprecipitates. The origins of nanoscalemagnetic inhomogeneity are discussed in terms of statistical variations in local composition and structure, tendency to chemical phase separation, and other forms of disorder.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lifetime measurements in the transitional nucleus {sup 138}Gd

Lifetime measurements have been made in the ground-state band of the transitional nucleus {sup 138}Gd from coincidence recoil-distance Doppler-shift data. {sup 138}Gd nuclei were produced using the {sup 106}Cd ({sup 36}Ar, 2p2n) reaction with a beam energy of 190 MeV. Reduced transition probabilities have been extracted from the lifetime data collected with the Koeln plunger placed at the target position of the JUROGAM-II array. The B(E2) values have been compared with predictions from X(5) critical-point calculations, which describe the phase transition between vibrational and axially symmetric nuclear shapes, as well as with IBM-1 calculations at the critical point. While the excitation energies in {sup 138}Gd are consistent with X(5) predictions, the large uncertainties associated with the measured B(E2) values cannot preclude vibrational and rotational contributions to the low-lying structure of {sup 138}Gd. Although experimental knowledge for the low-lying {gamma} and {beta}-vibrational bands in {sup 138}Gd is limited, potential-energy surface calculations suggest an increase in {gamma} softness in the ground-state band. In order to more fully account for the effects of {gamma} softness, the X(5) and IBM-1 calculations need to be extended to include the {gamma} degree of freedom for {sup 138}Gd.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

The Interior Angular Momentum of Core Hydrogen Burning Stars from Gravity-mode Oscillations

A major uncertainty in the theory of stellar evolution is the angular momentum distribution inside stars and its change during stellar life. We compose a sample of 67 stars in the core hydrogen burning phase with a log g value from high-resolution spectroscopy, as well as an asteroseismic estimate of the near-core rotation rate derived from gravity-mode oscillations detected in space photometry. This assembly includes 8 B-type stars and 59 AF-type stars, covering a mass range from 1.4 to 5 M {sub ⊙}, i.e., it concerns intermediate-mass stars born with a well-developed convective core. The sample covers projected surface rotation velocities vsin i∈[9,242] km s{sup −1} and core rotation rates up to 26 μHz, which corresponds to 50% of the critical rotation frequency. We find deviations from rigid rotation to be moderate in the single stars of this sample. We place the near-core rotation rates in an evolutionary context and find that the core rotation must drop drastically before or during the short phase between the end of the core hydrogen burning and the onset of core helium burning. We compute the spin parameter, which is the ratio of twice the rotation rate to the mode frequency (also known as the inverse Rossby number), for 1682 gravity modes and find the majority (95%) to occur in the sub-inertial regime. The 10 stars with Rossby modes have spin parameters between 14 and 30, while the gravito-inertial modes cover the range from 1 to 15.

79 ASTRONOMY AND ASTROPHYSICS↗

Density functional theory studies of HCOOH decomposition on Pd(111)

Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO 2 + H 2 and dehydration to CO + H 2 O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.

36 MATERIALS SCIENCE↗

Formation Pathway of Wurtzite-like Cu 2 ZnSnSe 4 Nanocrystals

Cu 2 ZnSnSe 4 is a direct band gap semiconductor composed of Earth-abundant elements, making it an attractive material for thin film photovoltaic technologies. Cu 2 ZnSnSe 4 crystallizes in the kesterite structure type as a bulk material, but it can also crystallize in a metastable wurtzite-like crystal structure when synthesized on the nanoscale. The wurtzite-like polymorph introduces unique and useful properties to Cu 2 ZnSnSe 4 materials, including widely tunable band gaps and superior composi-tional flexibility as compared to kesterite Cu 2 ZnSnSe 4 . Here, we investigate the formation pathway of colloidally prepared wurtzite-like Cu 2 ZnSnSe 4 nanocrystals. We show that this quaternary material forms through a chain of reactions, starting with binary Cu 3 Se 2 nanocrystals that, due to both kinetic and thermodynamic reasons, preferentially react with tin to yield hexagonal copper tin selenide intermediates. Furthermore, these ternary intermediates then react with zinc to form the resulting wurtzite-like Cu 2 ZnSnSe 4 nanocrystals. Based on this formation pathway, we suggest synthetic methods that may prevent the for-mation of unwanted impurity phases that are known to hamper the efficiency of Cu 2 ZnSnSe 4 -based optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinct pressure evolution of coupled nematic and magnetic orders in FeSe

We present a microscopic study of nematicity and magnetism in FeSe over a wide temperature and pressure range using high-energy x-ray diffraction and time-domain Mössbauer spectroscopy. The low-temperature magnetic hyperfine field increases monotonically up to ~6 GPa. The orthorhombic distortion initially decreases under increasing pressure but is stabilized at intermediate pressures by cooperative coupling to the pressure-induced magnetic order. Close to the reported maximum of the superconducting critical temperature at p = 6.8GPa, the orthorhombic distortion suddenly disappears and a new tetragonal magnetic phase occurs. As a result, the pressure and temperature evolution of the structural and magnetic order parameters suggests that they have distinct origins.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Unsupervised Learning Based Interaction Force Model for Nonspherical Particles in Incompressible Flows

This project provides a neural network-based interaction force model for gas-solid flows from low to intermediate Reynolds numbers and concentration, which can be linked to MFiX-DEM. We have constructed a database of the interaction force between the irregular-shaped particles using a spherical harmonic method and the fluid phase based on the particle-resolved direct numerical simulation (PR-DNS) with immersed boundary-based gas kinetic scheme. Unsupervised learning method, i.e., variational auto-encoder (VAE) has been applied to extract the primitive shape factors determining the drag force, lifting forces, and torque. The interaction force model has been trained and validated with a simple but effective multi-layer feed-forward neural network: multi-layer perceptron (MLP), which will be concatenated after the encoder of the previously trained VAE for geometry feature extraction for single, irregular particles. We have trained transpose convolutional neural networks with the PR-DNS data to predict the velocity and pressure gradient of the single particle systems and utilized them to calculate drag force of multi-particle systems. This model can provide high computational efficiency because it does not require collecting multiparticle system data from PR-DNS.

99 GENERAL AND MISCELLANEOUS↗

CGOLS V: Disk-wide Stellar Feedback and Observational Implications of the Cholla Galactic Wind Model

Abstract We present the fifth simulation in the Cholla Galactic OutfLow Simulation (CGOLS) project—a set of isolated starburst galaxy simulations modeled over large scales (10 kpc) at uniformly high resolution (Δx≈ 5 pc). Supernova feedback in this simulation is implemented as a disk-wide distribution of clusters, and we assess the impact of this geometry on several features of the resulting outflow, including the radial profiles of various phases; mass, momentum, and energy outflow rates; covering fraction of cool gas; mock absorption-line spectra; and X-ray surface brightness. In general, we find that the outflow generated by this model is cooler, slower, and contains more mass in the cool phase than a more centrally concentrated outflow driven by a similar number of supernovae. In addition, the energy loading factors in the hot phase are an order of magnitude lower, indicating much larger losses due to radiative cooling in the outflow. However, coupling between the hot and cool phases is more efficient than in the nuclear burst case, with almost 50% of the total outflowing energy flux carried by the cool phase at a radial distance of 5 kpc. These physical differences have corresponding signatures in observable quantities: the covering fraction of cool gas is much larger, and there is greater evidence of absorption in low and intermediate ionization energy lines. Taken together, our simulations indicate that centrally concentrated starbursts are more effective at driving hot, low-density outflows that will expand far into the halo, while galaxy-wide bursts may be more effective at removing cool gas from the disk.

Astronomy & Astrophysics↗

Stable carbon isotope fractionation by sulfate-reducing bacteria

Biogeochemical transformations occurring in the anoxic zones of stratified sedimentary microbial communities can profoundly influence the isotopic and organic signatures preserved in the fossil record. Accordingly, we have determined carbon isotope discrimination that is associated with both heterotrophic and lithotrophic growth of pure cultures of sulfate-reducing bacteria (SRB). For heterotrophic-growth experiments, substrate consumption was monitored to completion. Sealed vessels containing SRB cultures were harvested at different time intervals, and delta(13)C values were determined for gaseous CO(2), organic substrates, and products such as biomass. For three of the four SRB, carbon isotope effects between the substrates, acetate or lactate and CO(2), and the cell biomass were small, ranging from 0 to 2 per thousand. However, for Desulfotomaculum acetoxidans, the carbon incorporated into biomass was isotopically heavier than the available substrates by 8 to 9 per thousand. SRB grown lithoautotrophically consumed less than 3% of the available CO(2) and exhibited substantial discrimination (calculated as isotope fractionation factors [alpha]), as follows: for Desulfobacterium autotrophicum, alpha values ranged from 1.0100 to 1.0123; for Desulfobacter hydrogenophilus, the alpha value was 0.0138, and for Desulfotomaculum acetoxidans, the alpha value was 1.0310. Mixotrophic growth of Desulfovibrio desulfuricans on acetate and CO(2) resulted in biomass with a delta(13)C composition intermediate to that of the substrates. The extent of fractionation depended on which enzymatic pathways were used, the direction in which the pathways operated, and the growth rate, but fractionation was not dependent on the growth phase. To the extent that environmental conditions affect the availability of organic substrates (e.g., acetate) and reducing power (e.g., H(2)), ecological forces can also influence carbon isotope discrimination by SRB.

Deltaproteobacteria/growth & development/metabolis↗

Fabrication of uranium nitride

A method of producing uranium nitride (e.g., uranium mononitride) and/or uranium-containing intermediates that can be used to further produce uranium nitride includes reacting a reaction mixture comprising uranium carbide with a gas comprising hydrogen and nitrogen, cooling the reaction mixture to a temperature suitable to produce a phase comprising U2N3, and heating the reaction mixture to a temperature suitable to convert the phase comprising U2N3 to a phase comprising UN. The method produces highly purified UN, is insensitive to excess carbon reactants, and can be readily integrated into existing uranium production facilities as part of a continuous process.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Use of in-situ TEM to characterize the deformation-induced martensitic transformation in 304 stainless steel at cryogenic temperature

Highlights: • Unique experimental visualization of DIM transformation in 304SS in-situ in a TEM at cryogenic temperatures. • Three cases of DIM were captured in situ showing how stress and temperature are both effective on the transformation. • (i) formation of ε- martensite through overlapping/bundling of SFs (γ →SFs →ε), • (ii) direct (γ→ α’) transformation with interface migration upon pulling the sample at constant temperature, • (iii) direct γ→ α’ transformation upon cooling, without further pulling the sample. - Abstract: Tensile tests are conducted in-situ in a TEM at cryogenic temperatures (from − 100 °C to 0 °C) using a cooling TEM straining-stage with the goal of capturing the growth of the martensitic phase as it develops under stress in the material. The in-situ technique is used to explore the mechanism of deformation induced martensitic transformation in 304 and 304L austenitic stainless steels. The formation of stacking faults is captured, as well as the subsequent formation of ε-martensite, confirming the role played by Stacking faults (SFs) as intermediate step during the transformation from γ-austenite to ε-martensite. In addition, direct transformation from γ-austenite to α′-martensite is captured (i) upon straining at a fixed temperature and (ii) upon cooling after pulling on the sample, indicating how straining and temperature are both effective on the transformation.

36 MATERIALS SCIENCE↗