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

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At least 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Impact of ion fluxes across thylakoid membranes on photosynthetic electron transport and photoprotection

In photosynthetic thylakoid membranes the proton motive force (pmf) not only drives ATP synthesis, in addition it is central to controlling and regulating energy conversion. As a consequence, dynamic fine-tuning of the two pmf components, electrical (Δψ) and chemical (ΔpH), is an essential element for adjusting photosynthetic light reactions to changing environmental conditions. Good evidence exists that the Δψ/ΔpH partitioning is controlled by thylakoid potassium and chloride ion transporters and channels. However, a detailed mechanistic understanding of how these thylakoid ion transporter/channels control pmf partitioning is lacking. In this work, we combined functional measurements on potassium and chloride ion transporter and channel loss-of-function mutants with extended mathematical simulations of photosynthetic light reactions in thylakoid membranes to obtain detailed kinetic insights into the complex interrelationship between membrane energization and ion fluxes across thylakoid membranes. The data reveal that potassium and chloride fluxes in the thylakoid lumen determined by the K + /H + antiporter KEA3 and the voltage-gated Cl – channel VCCN1/Best1 have distinct kinetic responses that lead to characteristic and light-intensity-dependent Δψ/ΔpH oscillations. These oscillations fine-tune photoprotective mechanisms and electron transport which are particularly important during the first minutes of illumination and under fluctuating light conditions. By employing the predictive power of the model, we unravelled the functional consequences of changes in KEA3 and VCCN1 abundance and regulatory/enzymatic parameters on membrane energization and photoprotection.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2015

Representative Agricultural Pathways and Scenarios for Regional Integrated Assessment of Climate Change Impacts, Vulnerability, and Adaptation: Chapter - 5

The global change research community has recognized that new pathway and scenario concepts are needed to implement impact and vulnerability assessment where precise prediction is not possible, and also that these scenarios need to be logically consistent across local, regional, and global scales. For global climate models, representative concentration pathways (RCPs) have been developed that provide a range of time-series of atmospheric greenhouse-gas concentrations into the future. For impact and vulnerability assessment, new socio-economic pathway and scenario concepts have also been developed, with leadership from the Integrated Assessment Modeling Consortium (IAMC).This chapter presents concepts and methods for development of regional representative agricultural pathways (RAOs) and scenarios that can be used for agricultural model intercomparison, improvement, and impact assessment in a manner consistent with the new global pathways and scenarios. The development of agriculture-specific pathways and scenarios is motivated by the need for a protocol-based approach to climate impact, vulnerability, and adaptation assessment. Until now, the various global and regional models used for agricultural-impact assessment have been implemented with individualized scenarios using various data and model structures, often without transparent documentation, public availability, and consistency across disciplines. These practices have reduced the credibility of assessments, and also hampered the advancement of the science through model intercomparison, improvement, and synthesis of model results across studies. The recognition of the need for better coordination among the agricultural modeling community, including the development of standard reference scenarios with adequate agriculture-specific detail led to the creation of the Agricultural Model Intercomparison and Improvement Project (AgMIP) in 2010. The development of RAPs is one of the cross-cutting themes in AgMIP's work plan, and has been the subject of ongoing work by AgMIP since its creation.

agriculture↗
DOE OSTI2024

Direct cross-section measurement of the weak r -process Sr 88 ( α , n ) Zr 91 reaction in ν -driven winds of core-collapse supernovae

About half of the heavy elements beyond iron are known to be produced by the rapid neutron capture process, known as the r process. However, the astrophysical site producing the r process is still uncertain. Chemical abundances observed in several cosmic sites indicate that different mechanisms should be at play. For instance, the abundances around silver measured in a subset of metal-poor stars indicate the presence of a weak r process. This process may be active in neutrino-driven winds of core collapse supernovae where (α,n) reactions dominate the synthesis of Ζ ≈ 40 elements in the expelled materials. Scarcely measured, the rates of (α,n) reactions are determined from statistical Hauser-Feshbach calculations with α-optical-model potentials, which are still poorly constrained. Further, the uncertainties of the (α,n) reaction rates therefore make a significant contribution to the uncertainties of the abundances determined from stellar modeling. In this work, the 88 Sr (α,n)⁢ 91 Zr reaction which impacts the weak r-process abundances has been probed at astrophysics energy for the first time; directly measuring the total cross sections at astrophysical energies of 8.37–13.09 MeV in the center of mass (3.8–7.5 GK). Two measurements were performed at ATLAS with the electrically segmented ionization chamber MUSIC, in inverse kinematics, while following the active target technique. The cross sections of this α-induced reaction on 88 Sr, located at the shell closure N = 50, have been found to be lower than expected, by a factor of 3, despite recent statistical calculations validated by measurements on neighboring nuclei. This result encourages more experimental investigations of (α,n) reactions, at Ν = 50 and towards the neutron-rich side, to further test the predictive power and reliability of such calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

How the Bioinspired Fe 2 Mo 6 S 8 Chevrel Breaks Electrocatalytic Nitrogen Reduction Scaling Relations

The nitrogen reduction reaction (NRR) is a renewable alternative to the energy- and CO 2 -intensive Haber–Bosch NH 3 synthesis process but is severely limited by the low activity and selectivity of studied electrocatalysts. The Chevrel phase Fe 2 Mo 6 S 8 has a surface Fe–S–Mo coordination environment that mimics the nitrogenase FeMo-cofactor and was recently shown to provide state-of-the-art activity and selectivity for NRR. Here, we elucidate the previously unknown NRR mechanism on Fe 2 Mo 6 S 8 via grand-canonical density functional theory (GC-DFT) that realistically models solvated and biased surfaces. Fe sites of Fe 2 Mo 6 S 8 selectively stabilize the key *NNH intermediate via a narrow band of free-atom-like surface d-states that selectively hybridize with p-states of *NNH, which results in Fe sites breaking NRR scaling relationships. These sharp d-states arise from an Fe–S bond dissociation during N 2 adsorption that mimics the mechanism of the nitrogenase FeMo-cofactor. Furthermore, we developed a new GC-DFT-based approach for calculating transition states as a function of bias (GC-NEB) and applied it to produce a microkinetic model for NRR at Fe 2 Mo 6 S 8 that predicts high activity and selectivity, in close agreement with experiments. Furthermore, our results suggest new design principles that may identify effective NRR electrocatalysts that minimize the barriers for *N 2 protonation and *NH 3 desorption and that may be broadly applied to the rational discovery of stable, multinary electrocatalysts for other reactions where narrow bands of surface d-states can be tuned to selectively stabilize key reaction intermediates and guide selectivity toward a target product. Furthermore, our results highlight the importance of using GC-DFT and GC-NEB to accurately model electrocatalytic reactions.

10 SYNTHETIC FUELS↗
NASA NTRS2018

Greedy Sampling and Incremental Surrogate Model-Based Tailoring of Aeroservoelastic Model Database for Flexible Aircraft

This paper presents a data analysis and modeling framework to tailor and develop linear parameter-varying (LPV) aeroservoelastic (ASE) model database for flexible aircrafts in broad 2D flight parameter space. The Kriging surrogate model is constructed using ASE models at a fraction of grid points within the original model database, and then the ASE model at any flight condition can be obtained simply through surrogate model interpolation. The greedy sampling algorithm is developed to select the next sample point that carries the worst relative error between the surrogate model prediction and the benchmark model in the frequency domain among all input-output channels. The process is iterated to incrementally improve surrogate model accuracy till a pre-determined tolerance or iteration budget is met. The methodology is applied to the ASE model database of a flexible aircraft currently being tested at NASA/AFRC for flutter suppression and gust load alleviation. Our studies indicate that the proposed method can reduce the number of models in the original database by 67%. Even so the ASE models obtained through Kriging interpolation match the model in the original database constructed directly from the physics-based tool with the worst relative error far below 1%. The interpolated ASE model exhibits continuously-varying gains along a set of prescribed flight conditions. More importantly, the selected grid points are distributed non-uniformly in the parameter space, a) capturing the distinctly different dynamic behavior and its dependence on flight parameters, and b) reiterating the need and utility for adaptive space sampling techniques for ASE model database compaction. The present framework is directly extendible to high-dimensional flight parameter space, and can be used to guide the ASE model development, model order reduction, robust control synthesis and novel vehicle design of flexible aircraft.

numerical analysi↗
NASA NTRS1999

The Effect of Gravity Fields on Cellular Gene Expression

Early theoretical analysis predicted that microgravity effects on the isolated cell would be minuscule at the subcellular level; however, these speculations have not proven true in the real world. Astronauts experience a significant bone and muscle loss in as little as 2 weeks of spaceflight and changes are seen at the cellular level soon after exposure to microgravity. Changes in biological systems may be primarily due to the lack of gravity and the resulting loss of mechanical stress on tissues and cells. Recent ground and flight studies examining the effects of gravity or mechanical stress on cells demonstrate marked changes in gene expression when relatively small changes in mechanical forces or gravity fields were made. Several immediate early genes (IEG) like c-fos and c-myc are induced by mechanical stimulation within minutes. In contrast, several investigators report that the absence of mechanical forces during space flight result in decreased sera response element (SRE) activity and attenuation of expression of IEGs such as c-fos, c-jun and cox-2 mRNAs. Clearly, these early changes in gene expression may have long term consequences on mechanically sensitive cells. In our early studies on STS-56, we reported four major changes in the osteoblast; 1) prostaglandin synthesis in flight, 2) changes in cellular morphology, 3) altered actin cytoskeleton and 4) reduced osteoblast growth after four days exposure to microgravity. Initially, it was believed that changes in fibronectin (FN) RNA, FN protein synthesis or subsequent FN matrix formation might account for the changes in cytoskeleton and/ or reduction of growth. However our recent studies on Biorack (STS-76, STS-81 and STS-84), using ground and in-flight 1-G controls, demonstrated that fibronectin synthesis and matrix formation were normal in microgravity. In addition, in our most recent Biorack paper, our laboratory has documented that relative protein synthesis and mRNA synthesis are not changed after 24 hours exposure to microgravity. We did, however, find significant changes in osteoblast gene expression of IEGs, c-fos and cox-2 in microgravity exposure as compared to ground and in-flight 1-G controls. Subsequent ground studies suggest that the molecular mechanism underlying these changes may involve prostaglandin c-AMP receptors (EPs) and/or subsequent alteration of intracellular signaling in the absence of gravity.

Hughes-Fulford, Millie↗
NASA NTRS1998

Experimental Investigation of Organic Synthesis in Hydrothermal Environments

Seafloor hydrothermal systems may be the most likely locations on the early Earth for the emergence of life. Because of the disequilibrium inherent in such dynamic, mixing environments, abundant chemical energy would have been available for formation of the building blocks of life. In addition, theoretical studies suggest that organic compounds in these conditions would reach metastable states, due to kinetic barriers to the formation of stable equilibrium products (CO2 and methane). The speciation of organic carbon in metastable states is highly dependent on the oxidation state, pH, temperature, pressure and bulk composition of the system. The goal of our research is to investigate the effects of a number external variables on the formation, transformation, and stability of organic compounds at hydrothermal conditions. We have begun experimental work to attempt to control the oxidation state of simulated hydrothermal systems by using buffers composed of mineral powders and gas mixtures. We are also beginning to test the stability of organic compounds under these conditions. The experiments are being performed using the hydrothermal bomb apparatus at the U.S. Geological Survey in Menlo Park, CA and the supercritical water oxidizer (SCWO) at NASA Ames Research Center in Moffet Field, CA. The amino acids decomposed rapidly. Even after the approximately 15 minutes between addition of the amino acids and the first sampling, no amino acids were detected in the PPM system by GC- MS, while in the FeFeO system the amino acids were present at a level of less than 50% of original. Carboxylic acids, ammonia, and CO2 were the main products, along with some unidentified compounds. The ratios of carboxylic acids and concentrations of other products seem to have remained stable during the experiments, consistent with observations of other metastable systems and theoretical predictions.

Shock, Everett L.↗
NASA NTRS1999

Chain Dynamics in Magnetorheological Suspensions

Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.

Gast, A. P.↗
DOE OSTI2025

Accurate and uncertainty-aware multi-task prediction of HEA properties using prior-guided deep Gaussian processes

Surrogate modeling techniques have become indispensable in accelerating the discovery and optimization of high-entropy alloys (HEAs), especially when integrating computational predictions with sparse experimental observations. This study systematically evaluates the training and testing performance of four prominent surrogate models—conventional Gaussian processes (cGP), Deep Gaussian processes (DGP), encoder-decoder neural networks for multi-output regression and eXtreme Gradient Boosting (XGBoost)—applied to a hybrid dataset of experimental and computational properties of the 8-component HEA system Al-Co-Cr-Cu-Fe-Mn-Ni-V. We specifically assess their capabilities in predicting correlated material properties, including yield strength, hardness, modulus, ultimate tensile strength, elongation, and average hardness under dynamic/quasi-static conditions, alongside auxiliary computational properties. The comparison highlights the strengths of hierarchical deep modeling approaches in handling heteroscedastic, heterotopic, and incomplete data commonly encountered in materials science. Our findings illustrate that combined surrogate models such as DGPs infused with machine-learned priors outperform other surrogates by effectively capturing inter-property correlations and by assimilating prior knowledge. This enhanced predictive accuracy positions the combined surrogate models as powerful tools for robust and data-efficient materials design.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Solid State Reduction Driven Synthesis of Mn Containing Multi-principal Component Alloys

In recent years, high entropy alloys (HEAs), also known as multi-principal component alloys (MPCAs) have emerged as a new and exciting class of materials. This paper reports on the solid state reduction synthesis of a series of CoFeNiMn-based MPCA compositions, starting from a mixture of the corresponding oxides. One of the aims of the study was to test whether the degree of reduction of MnO, a highly stable oxide, could be enhanced by tailoring the alloy composition. Specifically, the influence of Ni content was studied because Ni exhibits a significant negative enthalpy of mixing with Mn. High purity precursor powders of Co(OH) 2 , Fe 2 O 3 , MnO 2 , and NiO were milled and mixed using standard ceramic processing methods. Here, the nominal sample compositions (assuming complete oxide reduction) were (CoFeMn) x Ni (1-x) , for x = 0, 0.083, 0.166, and 0.25. The oxide samples were subjected to a series of isothermal reduction anneals in flowing 3 pct H 2 –Ar at 1100 °C. The resulting microstructures were characterized using scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The composition of the resulting MPCAs was determined quantitatively using wavelength dispersive spectroscopy (WDS) in the electron microprobe. The study revealed that for each of the initial oxide compositions studied, it was possible to achieve an MPCA with ~ 25 at. pct Mn. These results were found to be consistent with the predictions of a thermodynamic model whereby a negative enthalpy of mixing (ΔH mix ), combined with a contribution from configurational entropy, can offset a positive free energy of reduction (ΔG red ). The incorporation of vibrational entropy into first principles calculations was found to have a significant effect on the predicted crystal structure of the MPCAs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dynamics of poly[n]catenane melts

Inspired by advances in the chemical synthesis of interlocking polymer architectures, extensive molecular dynamics simulations have been conducted to study the dynamical properties of poly[n]catenanes-polymers composed entirely of interlocking rings-in the melt state. Both the degree of polymerization (number of links) and the number of beads per ring are systematically varied, and the results are compared to linear and ring polymers. Herein, a simple Rouse-like model is presented, and its analytical solution suggests a decomposition of the dynamics into "ring-like" and "linear-like" regimes at short and long times, respectively. In agreement with this picture, multiple sub-diffusive regimes are observed in the monomer mean-squared-displacements even though interchain entanglement is not prevalent in the system. However, the Rouse-type model does not account for the topological effects of the mechanical bonds, which significantly alter the dynamics at intermediate length scales both within the rings and at the chain segment scales. The stress relaxation in the system is extremely rapid and may be conveniently separated into ring-like and linear-like contributions, again in agreement with the Rouse picture. However, the viscosity has a non-monotonic dependence on the ring size for long chains, which disagrees strongly with theoretical predictions. This unexpected observation cannot be explained in terms of chain disentanglement and is inconsistent with other measures of polymer relaxation. Possible mechanisms for this behavior are proposed and implications for materials design are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Experimental measurement of the rapid mixing of fuel and air in a multi-element diffusion (Hencken) burner

Flat flame burners are valuable tools for studying complex combustion phenomena like particle synthesis due to the well-controlled and well-behaved initial and boundary conditions. In this study, the methane/air flame temperature and tracer density profiles of a multi-element diffusion burner equipped with a central tube were characterized using krypton (Kr) x-ray fluorescence at the Advanced Photon Source at Argonne National Laboratory. The experiments were performed using a fuel-to-oxygen equivalence ratio of 0.8 and 3.3% Kr by volume was added to the reactant gases. One- and two-dimensional scans of non-combusting (i.e., cold flow) and combusting conditions, both with and without flow through the central tube were performed. Spatially-resolved Kr number density profiles were obtained at different planar locations and heights above the surface of the burner. The results show rapid mixing occurred near the exit-plane of the burner and increased spatial uniformity was achieved from 0.1 mm to 0.5 mm above the surface of the burner. Further, the data also showed the impact of the central tube flow on the main methane/air flame, including evidence of the central tube flow mixing with the main flow. Flame temperatures were calculated from the fluorescence measurements at various heights above the burner surface and were in good agreement with model predictions for a burner stabilized flame. These high-fidelity measurements provide accurate baseline data that are particularly valuable for understanding the effects of fuel and air mixing on downstream phenomena, such as the formation of condensed-phase products.

42 ENGINEERING↗
DOE OSTI2026

Exploring the fusion power plant design space: comparative analysis of positive and negative triangularity tokamaks through optimization

The optimal configuration choice between positive triangularity (PT) and negative triangularity (NT) tokamaks for fusion power plants hinges on navigating different operational constraints rather than achieving specific plasma performance metrics. This study presents a systematic comparison using constrained multi-objective optimization with the integrated FUsion Synthesis Engine (FUSE) framework. Over 200 000 integrated design evaluations were performed exploring the trade-offs between capital cost minimization and operational reliability (maximizing q 95 ) while satisfying engineering constraints including 250 ± 50 MW net electric power, tritium breeding ratio > 1.1, power exhaust limits and an hour flattop time. Both configurations achieve similar cost-performance Pareto fronts through contrasting design philosophies. PT, while demonstrating resilience to pedestal degradation (compensating for up to 40% reduction), are constrained to larger machines (R 0 > 6.5 m) by the narrow operational window between L–H threshold requirements and the research-established power exhaust limit (P sol /R < 15 MW m –1 ). This forces optimization through comparatively reduced magnetic field (∼8 T). NT configurations exploit their freedom from these constraints to access compact, high-field designs (R 0 ~ 5.5 m, B 0 >12 T), creating natural synergy with advancing HTS technology. Sensitivity analyses reveal that PT’s economic viability depends critically on uncertainties in L–H threshold scaling and power handling limits. Notably, a 50% variation in either could eliminate viable designs or enable access to the compact design space. These results suggest configuration selection should be risk-informed: PT offers the lowest-cost path when operational constraints can be confidently predicted, while NT is robust to large variations in constraints and physics uncertainties.

FUSE framework↗
DOE OSTI2020

Synthesis and structural characterization of the new Zintl phases Ba 3 Cd 2 P 4 and Ba 2 Cd 2 P 3 . Rare example of small gap semiconducting behavior with negative thermopower within the range 300 K-700 K

The new Zintl phases Ba 3 Cd 2 P 4 and Ba 2 Cd 2 P 3 have been synthesized using Pb flux, which allowed for the growth of 4-5 mm large crystals. The structures were determined utilizing single-crystal X-ray diffraction methods. Both compounds crystalize in the monoclinic crystal system (space group C2/m (No. 12)) and their structures are closely related. The structure of Ba 3 Cd 2 P 4 can be seen as being comprised of divalent Ba atoms and conjoined CdP 4 tetrahedra in the form of [Cd 2 P 4 ] 6- layers. Within the layers, homoatomic P–P bonds are present, which if cleaved, leave two infinite [CdP 3 ] 7- chains running along the crystallographic b-axis. The other structure, that of Ba 2 Cd 2 P 3 , can be rationalized as also having divalent Ba atoms and conjoined CdP4 tetrahedra in the form of [Cd 2 P 3 ] 6- layers. These layers, again, can be visualized as chains that run down the crystallographic b-axis, which are further connected by P-P dimers. Electronic band structure calculations show that each structure has an optimal number of valence electrons, and therefore conform to the Zintl-Klemm concept. Accordingly, the two compounds can be considered small band gap semiconductors, with band gaps of ca. 0.1 eV and 0.6 eV for Ba3Cd2P4 and Ba 2 Cd 2 P 3 , respectively. Electrical resistivity measurements show that Ba3Cd2P4 displays a large resistivity value at room temperature and an experimental band gap of ca. 0.05 eV, which fits reasonably well with the theoretical predictions. Thermopower measurements show that throughout the temperature range 300 K-700 K, Ba 3 Cd 2 P 4 displays a negative Seebeck coefficient. Here, the extremum value of -84 μV is reached at 630 K, suggestive of an n-type semiconductor, a rarity among Zintl phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Molecular Simulations Probing the Adsorption and Diffusion of Ammonia, Nitrogen, Hydrogen, and Their Mixtures in Bulk MFI Zeolite and MFI Nanosheets at High Temperature and Pressure

Recent advances in the synthesis of MFI zeolite nanosheets have led to highly selective membranes that are promising candidates for small-scale ammonia separation from ammonia/nitrogen/hydrogen mixtures in distributed green ammonia production plants. Using force-field-based molecular simulations, we evaluate the performance of bulk all-silica MFI zeolite and a 3 nm thick all-silica MFI nanosheet for ammonia/nitrogen/hydrogen separations at moderate temperature and pressure conditions (T = 373 K, p = 5 bar) as well as conditions relevant for a membrane-based reactor–separator process (T = 523 or 623 K, p = 80 bar). Isobaric–isothermal Gibbs ensemble Monte Carlo (GEMC) simulations were carried out to understand the selective adsorption behavior for these mixtures. Molecular dynamics simulations in the canonical ensemble were performed to examine the transport behavior of ammonia in a mixture with nitrogen or hydrogen at loadings obtained from the GEMC simulations. Our results show that both bulk MFI and the nanosheet with explicit surface silanols are highly selective toward ammonia adsorption, but the adsorption selectivity decreases by factors of 4 and 10 for ammonia/nitrogen and ammonia/hydrogen mixtures as the temperature is increased from 373 to 623 K. Conversely, the diffusion selectivities toward ammonia are more favorable at process-relevant temperatures and for the MFI nanosheet. Here, at T = 523 K and p = 80 bar, our simulations predict overall separation factors of 3.8 ± 0.2 and 4.5 ± 0.3 for ammonia/nitrogen and ammonia/hydrogen mixtures, respectively, in the bulk MFI zeolite, and separation factors of 8.6 ± 0.4 and 12.5 ± 0.8, respectively, for the MFI nanosheet.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Controls and relationships of soil organic carbon abundance and persistence vary across pedo–climatic regions

One of the largest uncertainties in the terrestrial carbon cycle is the timing and magnitude of soil organic carbon (SOC) response to climate and vegetation change. This uncertainty prevents models from adequately capturing SOC dynamics and challenges the assessment of management and climate change effects on soils. Reducing these uncertainties requires simultaneous investigation of factors controlling the amount (SOC abundance) and duration (SOC persistence) of stored C. We present a global synthesis of SOC and radiocarbon profiles (n Profile = 597) to assess the timescales of SOC storage. We use a combination of statistical and depth–resolved compartment models to explore key factors controlling the relationships between SOC abundance and persistence across pedo–climatic regions and with soil depth. This allows us to better understand (i) how SOC abundance and persistence covary across pedo–climatic regions and (ii) how the depth dependence of SOC dynamics relates to climatic and mineralogical controls on SOC abundance and persistence. We show that SOC abundance and persistence are differently related; the controls on these relationships differ substantially between major pedo–climatic regions and soil depth. For example, large amounts of persistent SOC can reflect climatic constraints on soils (e.g., in tundra/polar regions) or mineral absorption, reflected in slower decomposition and vertical transport rates. In contrast, lower SOC abundance can be found with lower SOC persistence (e.g., in highly weathered tropical soils) or higher SOC persistence (e.g., in drier and less productive regions). We relate variable patterns of SOC abundance and persistence to differences in the processes constraining plant C input, microbial decomposition, vertical C transport and mineral SOC stabilization potential. This process–oriented grouping of SOC abundance and persistence provides a valuable benchmark for global C models, highlighting that pedo–climatic boundary conditions are crucial for predicting the effects of climate change and soil management on future C abundance and persistence.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1995

Ultraviolet radiation from evolved stellar populations. 2: The ultraviolet upturn phenomenon in elliptical galaxies

We discuss the far-ultraviolet upturn phenomenon (UVX) observed in elliptical galaxies and spiral galaxy bulges. Our premise is the UV radiation from these systems emanates primarily from extreme horizontal branch (EHB) stars and their progeny. We derive the broad-band UV colors 1500-V and 2500-V for globular clusters and elliptical galaxies from the available satellite data and investigate color-color and color-line strength correlation. Clusters can be bluer than any galaxy in 15-V and 25-V, implying larger hot star populations, but galaxies are significantly bluer than clusters in 15-25 at a given 15-V. We attribute this primarily to the effect of metal abundance on the mid-UV (2500 A) light. These redder colors of the galaxies also imply that the UVX in galaxies is not produced by metal-poor subpopulations similar to the clusters. We devlop a simple spectral synthesis formulation for all phases of single star evolution from the zero-age main sequence (ZAMS) to the white dwarf cooling track that requires only one or two parameters for each choice of age and abundance. We provide the ingredients necessary for constructing models with arbitrary horizontal branch (HB) morphologies in the age range 2 less than t less than 20 Gyr and for six metallicities in the range -2.26 less than (Fe/H) less than 0.58; we also consider the efect of enhanced Y in metal-rich models. The maximum lifetime UV output is produced by EHB stars with (M(sub env))(sup 0) approximately 0.02 solar mass and can be up to 30 times higher than for post-asymptotic giant branch (P-AGB) stars. The ultraviolet output of old populations is governed primarily by the distribution of (M(sub env))(sup 0)P(M(sub env))(sup 0), on the ZAHB. The UV output is not very sensitive to (Fe/H) or to Y, but it can change very rapidly with (M(sub env))(sup 0). Thus it is extremely sensitive to the precise nature of giant-branch mass loss. Our models use simple descriptions of P(M(sub env))(sup 0) to bracket the colors produced from any real distribution of stars. Our models accurately predict the range of UV colors observed for the globular clusters, given known constraints on their age, abundances, and HB morphologies. We find that models with (Fe/H) greater than or = 0 that do not contain EHB stars cannot reproduce the colors of most of the galaxies. The models also predict that the fraction of the far-UV light from P-AGB stars, which are spatially resolvable in nearby galaxies, is approximately 70% and approximately 20% for moderate UVX and strong UVX systems, respectively. We find that 25-V, but not 15-V, is sensitive to the age and abundance, though these cannot always be cleanly distinguished. The galaxy colors place limits of (Fe/H) greater than -0.5 and less than 15% on the contribution of globular cluster-type populations to the V light. Galaxy colors are consistent with solar-abundance models with ages in the range 6-14 Gyr. We discuss several implications of the observations and the models, including the question of light metal versus iron peak enhancements in galaxies, whether the UV color-Mg(sub 2) correlation is continuous or discrete, effects of helium abundnace on the UVX, and the key question of whether red giant branch mass loss can be large enough to produce the necessary EHB population in the strong UVX galaxies.

Dorman, Ben↗
NASA NTRS2022

Ultraviolet Spectropolarimetry: on the Origin of Rapidly Rotating B Stars

UV spectroscopy and spectropolarimetry hold the key to understanding certain aspects of massive stars that are largely inaccessible (or exceptionally difficult) with optical or longer wavelength observations. As we demonstrate, this is especially true for the rapidly-rotating Be and Bn stars, owing to their high temperatures, geometric asymmetries, binary properties, evolutionary history, as well as mass ejection and disks (in the case of Be stars). UV spectropolarimetric observations are extremely sensitive to the photospheric consequences of rapid rotation (i.e. oblateness, temperature, and surface gravity gradients), far beyond the reach of optical wavelengths. Our polarized radiative-transfer modelling predicts that with low-resolution UV spectropolarimetry covering 120–300 nm, and with a reasonable SNR, the inclination angle of a rapid rotator can be determined to within 5 degrees, and the rotation rate to within 1%. The origin of rapid rotation in Be/n stars can be explained by either single-star or binary evolution, but their relative importance is largely unknown. Some Be stars have hot sub-luminous (sdO) companions, which at an earlier phase transferred their envelope (and with it mass and angular momentum) to the present-day rapid rotator. Although sdO stars are small and relatively faint, their flux peaks in the UV making this the optimal observational wavelength regime. Through spectral modelling of a wide range of simulated Be/n+sdO configurations, we demonstrate that high-resolution high-signal-to-noise ratio UV spectroscopy can detect an sdO star even when ∼1,000 times fainter in the UV than its Be/n star companion. This degree of sensitivity is needed to more fully explore the parameter space of Be/n+sdO binaries, which so far has been limited to about a dozen systems with relatively luminous sdO stars. We suggest that a UV spectropolarimetric survey of Be/n stars is the next step forward in understanding this population. Such a dataset would, when combined with population synthesis models, allow for the determination of the relative importance of the possible evolutionary pathways traversed by these stars, which is also crucial for understanding their future evolution and fate.

Ultraviolet astronomy↗