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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 1,459 records · Page 81
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

H–D exchange between quercetin and solvent in the presence of Au{sup I} chloride complexes with DMSO: quantum chemical modeling

The pathways of H–D exchange between quercetin and solvent taking into account the effects of the medium are considered using quantum chemical calculations and the mechanism of selective H–D exchange reaction at the C(2′) position observed only in the presence of Au complexes is identified. It is shown that only the exchange processes in the A-ring have suffi- ciently low activation barriers. In the acidic and alkaline media, these processes occur at lower energies as compared with the reaction in the neutral system, which qualitatively agrees with the published experimental data. It was shown that the Au{sup I} chloride complex with DMSO is able to react with the C–H bond at the C(2′) position by the mechanism of electrophilic substitution under mild conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

(Project 14-6770) An Investigation to Establish Multiphysical Property Dataset of Nuclear Materials Based on in-situ Observations and Measurements

In-core nuclear materials including fuel pins and cladding materials fail due to issues including corrosion, mechanical wear, and pellet cladding interaction. In most such scenario microstructure dependent and corrosioninduced chemistry dependent property changes significantly affect performance of cladding, pellet, and housing. Emphasis of this work was on replace conventional pellet-cladding material models with a new straingradient viscoplasticity model that is informed by transmission electron microscopy (TEM) based measurements and by nanomechanical Raman spectroscopy (NMRS) based measurements. The TEM measurements are quantitative in nature and therefore reveal stress-strain relations with simultaneous insights into mechanisms of deformation at nanoscale. The NMRS measurements reveal the similar information at mesoscale along with additional information on relating local microstructural stresses with applied stresses. The resulting information is used to fit constants in the strain gradient viscoplasticity model as well as to validate one. During TEM measurements, a micro-electro-mechanical system based setup was developed with mechanical actuation, sensing, heating, and electrical loading. Contrary to post-mortem analysis or qualitative visualization, this setup combines direct visualization of the mechanisms behind deformation with measurement of stress, strain, thermal and electrical properties. The unique research philosophy of visualizing the microstructure at high resolution while measuring the properties led to fundamental understanding in grain size and temperature effects on measured mechanical properties such as fracture toughness. A key contribution is the role of mechanical loading boundary conditions to deconvolute the insitu TEM based nanoscale and NMRS based mesoscale data to bulk behavior. First the literature based pellet cladding mechanical interaction model based on the work of Retel’s and Williamson’s in literature work to predict tempurature and stress distribution in cladding and pellet at normal operating condition was analyzed. Later the data was fitted to find constants for a viscoplastic strain gradient model. The developed model still needs to be refined and calibrated using various experimental results. That remains the focus of future work. Overall, a major thrust of the work was therefore on active control of the microstructure (grain size, defect density and types) exploiting the multi-physics coupling in materials. In particular, using experiments the synergy of current density, mechanical stress and temperature were studied to annihilate defects and recrystallize grains. The developed model is being examined for implementation in BISON. Multiple invited talks, international journal publications, and conference publications were performed by students supported on this work. Another output is support multiple PhD and masters thesis students who will be an important asset for future basic nuclear research. Future Work Recommendations: A nuclear reactor operates under significant variations of thermal loads due to energy cycling and mechanical loads due to constraint effects. Significant thermal and chemical diffusion takes place at the pallet-cladding level. While the proposed work established new experimental approach and new dataset for Zircaloy-4, the irradiation level was in the range of 1-2 dpa. Samples with higher dpa need to be examined. Therefore, a continual of support of the performed work is essential. Currently, these are the only experiments that can measure the produced data. The work also needs to be extended to different fuel types and cladding types such as SiC and FeCrAl based claddings. A combination of datasets for these materials can then be used to analyze accurately predict behavior of critical pellet cladding systems in accident scenario with high heat flux and high thermal loads. This is a BIG unknown as if now.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Thermo-physical Properties of U-10Mo Monolithic Fuel

Monolithic fuel is a candidate fuel form that is being considered for the conversion of high-performance research reactors. This plate-type fuel consists of a high-density, U-Mo fuel in a monolithic form that is sandwiched between zirconium diffusion barriers and encapsulated in an aluminum cladding. To date, many plates were irradiated with a satisfactory irradiation performance, demonstrating that the conceptual design works. The program is now moving to the qualification phase, a predecessor to the timely conversion of the target reactors. To qualify this fuel system, the program must show that the fuel plates have predictable behavior, meet the safety standards, and perform well in reactors. The requirement of a satisfactory irradiation performance under normal operating conditions is primarily demonstrated by a successful testing. To demonstrate that the fuel system has a predictable behavior, the several key material properties should be quantified accurately since these properties are needed to estimate the thermal and mechanical behavior of the fuel system. Although, there is a large set of thermophysical property data available for unirradiated material, the property data for irradiated fuel is scarce. Since irradiation causes drastic effects in material, a significant change in material properties occurs. Consequently, using representative degradation models becomes essential for accurate performance assessments. This work examines thermal conductivity of U-10Mo, by evaluating recent experimental data from the literature and available theoretical models. The study has discovered inconsistencies in the literature data, revealing that previously developed theoretical models fail to predict the thermal conductivity of irradiated fuel.

42 ENGINEERING↗
DOE OSTI2022

Melting and phase relations of Fe-Ni-Si determined by a multi-technique approach

Many studies have suggested silicon as a candidate light element for the cores of Earth and Mercury. However, the effect of silicon on the melting temperatures of core materials and thermal profiles of cores is poorly understood, due to disagreements among melt detection techniques, uncertainties in sample pressure evolution during heating, and sparsity of studies investigating the combined effects of nickel and silicon on the phase diagram of iron. Here, in this study we develop a multi-technique approach for measuring the high-pressure melting and solid phase relations of iron alloys and apply it to Fe 0.8 Ni 0.1 Si 0.1 (Fe-11wt%Ni-5.3wt%Si), a composition compatible with recent estimates for the cores of Earth and Mercury. This approach combines results (20-83 GPa) from two atomic-level techniques: synchrotron Mossbauer spectroscopy (SMS) and synchrotron x-ray diffraction (XRD). Melting is independently detected by the loss of the Mossbauer signal, produced exclusively by solid-bound iron nuclei, and the onset of a liquid diffuse x-ray scattering signal. The use of a burst heating and background updating method for quantifying changes in the reference background during heating facilitates the determination of liquid diffuse signal onsets and leads to strong reproducibility and excellent agreement in melting temperatures determined separately by the two techniques. XRD measurements additionally constrain the hcp-fcc phase boundary and in-situ pressure evolution of the samples during heating. We apply our updated thermal pressure model to published SMS melting data on fcc-Fe and fcc-Fe 0.9 Ni 0.1 to precisely evaluate the effect of silicon on melting temperatures. We find that the addition of 10 mol% Si to Fe 0.9 Ni 0.1 reduces melting temperatures by ~250 K at low pressures (<60 GPa) and flattens the hcp-fcc phase boundary. Extrapolating our results, we constrain the location of the hcp-fcc-liquid quasi-triple point at 147±14 GPa and 3140±90 K, which implies a melting temperature reduction of 500 K compared with Fe 0.9 Ni 0.1 . The results demonstrate the advantages of combining complementary experimental techniques in investigations of melting under extreme conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thermal properties of U-Mo alloys irradiated under high fission power density

A variety of physical and thermal property measurements made on irradiated U-Mo alloy monolithic fuel samples with a Zr diffusion barrier and clad in Al alloy 6061 are reported. These properties form the basis for additional investigations in thermal behavior of U-Mo fuel under high performance research reactor irradiation conditions. Measurements were performed on samples harvested from fuel plates irradiated under high fission power density and surface heat flux and complement previous measurements on samples subjected to moderate fission power density and surface heat flux. Specific heat capacity of irradiated monolithic U-Mo increases with increasing temperature and fission density, but carries large uncertainties associated with thickness measurements used to determine the mass fraction of the layer constituents for extraction of the U-Mo specific heat capacity, specifically the very thin and nonuniform Zr diffusion barrier. Density of irradiated monolithic U-Mo decreases with increasing fission density resulting from fission gas swelling and porosity formation. Thermal diffusivity of irradiated monolithic U-Mo increased with increasing temperature and decreased with increasing fission density. Thermal conductivity of irradiated monolithic U-Mo increased with increasing temperature, and in general, appeared to decrease and become less sensitive to temperature with increasing fission density. Thermal conductivity measurements compared to a semi-empirical model agreed within ±30%. It is suspected that the main driver in deviation between model calculations and measurements is the fission gas swelling determination, which does not account for fission power density or irradiation temperature.

uranium (U), molybdenum, nuclear fuel, thermal con↗
DOE OSTI2016

Numerical study of turbulence-influence mechanism on arc characteristics in an air direct current circuit breaker

This paper focuses on the numerical investigation of arc characteristics in an air direct current circuit breaker (air DCCB). Using magneto-hydrodynamics (MHD) theory, 3D laminar model and turbulence model are constructed and calculated. The standard k-epsilon model is utilized to consider the turbulence effect in the arc chamber of the DCCB. Several important phenomena are found: the arc column in the turbulence-model case is more extensive, moves much more slowly than the counterpart in the laminar-model case, and shows stagnation at the entrance of the chamber, unlike in the laminar-model case. Moreover, the arc voltage in the turbulence-model case is much lower than in the laminar-model case. However, the results in the turbulence-model case show a much better agreement with the results of the breaking experiments under DC condition than in the laminar-model case, which is contradictory to the previous conclusions from the arc researches of both the low-voltage circuit breaker and the sulfur hexafluoride (SF6) nozzle. First, in the previous air-arc research of the low-voltage circuit breaker, it is assumed that the air plasma inside the chamber is in the state of laminar, and the laminar-model application gives quite satisfactory results compared with the experiments, while in this paper, the laminar-model application works badly. Second, the turbulence-model application in the arc research of the SF6-nozzle performs much better and gives higher arc voltage than the laminar-model application does, whereas in this paper, the turbulence-model application predicts lower arc voltage than the laminar-model application does. Based on the analysis of simulation results in detail, the mechanism of the above phenomena is revealed. The transport coefficients are strongly changed by turbulence, which will enhance the arc diffusion and make the arc volume much larger. Consequently, the arc appearance and the distribution of Lorentz force in the turbulence-model case substantially differ from the arc appearance and the distribution of Lorentz force in the laminar-model case. Thus, the moving process of the arc in the turbulence-model case is slowed down and slower than in the laminar-model case. Moreover, the more extensive arc column in the turbulence-model case reduces the total arc resistance, which results in a lower arc voltage, more consistent with the experimental results than the arc voltage in the laminar-model case. Therefore, the air plasma inside this air DCCB is believed to be in the turbulence state, and the turbulence model is more suitable than the laminar model for the arc simulation of this kind of air DCCB.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Large-scale molecular dynamics simulations of bubble collapse in water: Effects of system size, water model, and nitrogen

Molecular dynamics simulations in the microcanonical ensemble are performed to study the collapse of a bubble in liquid water using the single-site mW and the four-site TIP4P/2005 water models. To study system size effects, simulations for pure water systems are performed using periodically replicated simulation boxes with linear dimensions, L, ranging from 32 to 512 nm with the largest systems containing 8.7 × 10 6 and 4.5 × 10 9 molecules for the TIP4P/2005 and mW water models, respectively. The computationally more efficient mW water model allows us to reach converging behavior when the bubble dynamics results are plotted in reduced units, and the limiting behavior can be obtained through linear extrapolation in L –1 . Qualitative differences are observed between simulations with the mW and TIP4P/2005 water models, but they can be explained by the models’ differences in predicted viscosity and surface tension. Although bubble collapse occurs on time scales of only hundreds of picoseconds, the system sizes used here are sufficiently large to obtain bubble dynamics consistent with the Rayleigh–Plesset equation when using the models’ thermophysical properties as input. For the conditions explored here, extreme heating of the interfacial water molecules near the time of collapse is observed for the larger mW water systems (but the model underpredicts the viscosity), whereas heating is less pronounced for the TIP4P/2005 water systems because its larger viscosity contribution slows the collapse dynamics. The presence of nitrogen within the bubble only starts to affect bubble dynamics near the very end of the initial collapse, leading to an incomplete collapse and strong rebound for the mW water model. Although nitrogen is non-condensable at 300 K, it becomes highly compressed and reaches a liquid-like density near the collapse point. We find that the dissolution of nitrogen is much slower than the movement of the collapsing water front, and the re-expansion of the dense nitrogen droplet gives rise to bubble rebound. The incompatibility of the collapse and dissolution time scales should be considered for continuum-scale modeling of bubble dynamics. Finally, we also confirm that the diffusion coefficient for dissolved nitrogen is insensitive to pressure as the liquid transitions from a compressed to a stretched state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

The mobility of small vacancy/helium complexes in tungsten and its impact on retention in fusion-relevant conditions

Tungsten is a promising plasma facing material for fusion reactors. Despite many favorable properties, helium ions incoming from the plasma are known to dramatically affect the microstructure of tungsten, leading to bubble growth, blistering, and/or to the formation of fuzz. In order to develop mitigation strategies, it is essential to understand the atomistic processes that lead to bubble formation and subsequent microstructural changes. In this work, we use large-scale Accelerated Molecular Dynamics simulations to investigate small (N=1,2) V N He M vacancy/helium complexes, which serve as the nuclei for larger helium bubble growth, over timescales reaching into the milliseconds under conditions typical of the operation of fusion reactors. These complexes can interconvert between different I L V N+L He M variants via Frenkel pair nucleation (leading to the creation of a additional vacancy/interstitial pair) and annihilation events; sequences of these events can lead to net migration of these embryonic bubbles. The competition between nucleation and annihilation produces a very complex dependence of the diffusivity on the number of heliums. Finally, through cluster dynamics simulations, we show that diffusion of these complexes provides an efficient pathway for helium release at fluxes expected in fusion reactors, and hence that accounting for the mobility of these complexes is crucial.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hole Polaron Transport in Bismuth Vanadate BiVO 4 from Hybrid Density Functional Theory

In this paper, we address the chemical character and the mobility of hole polarons in BiVO 4 (BVO). Two distinct structures for hole polarons in BVO have been reported in the literature to date. “Standard” hybrid density functional theory (DFT) calculations have predicted hole polarons to be (BiO 8 ) dodecahedron-centered polarons, while Hubbard U-DFT (DFT + U) calculations have predicted single oxygen atom-centered polarons. Resolving these contrasting findings is critical to validate theory in materials research. We investigated the structure of hole polarons in BVO using hybrid DFT with varying fractions (α) of the exact exchange interaction that enters hybrid functionals. For values of the fraction α, from α = 0.25 to α = 0.45, we obtained both structures, the h + (BiO 8 ) hole structure and the h + (O) hole structure. For the smaller values of α, the h + (BiO 8 ) structure is lower in energy, while for the larger values of α, the h+(O) structure is more stable. The piece-wise linearity of DFT energies E(q) with respect to a point defect charge q is maintained satisfactorily in all cases, although the deviation is the smallest for hybrid DFT with a small exact exchange fraction. For α = 0.25, we determined the diffusivity of h + (BiO 8 ) holes from the Marcus/Holstein two-state model. The activation barrier for Bi-to-Bi hops (ΔG # ~76 meV) and mobility (μ ~0.029 cm2 V –1 s –1 ) are found to be in close agreement with the published THz experimental data (ΔG # ~90 meV and μ exp ~0.02 cm2 V –1 s –1 , respectively). In h + (BiO 8 ) structures, nearly 25% of the hole charge and unpaired spin reside on the Bi atom and the rest is divided among the eight O atoms. The hole is best described as a Bi-centered hole, rather than a Bi 6s hole. In contrast, in h + (O) structures, about 75% of the unpaired spin population resides on the O atom. These findings suggest that if one wishes to resolve this theoretical dichotomy, there remains a need for further experimental characterization of hole polarons in BVO with techniques that could identify the oxidation state of Bi and O atoms in operando conditions and help validate theoretical results of structure and transport.

14 SOLAR ENERGY↗
DOE OSTI2018

Technetium Stabilization in Low-Solubility Sulfide Phases: A Review

We report that technetium contamination remains a major environmental problem at nuclear reprocessing sites, e.g., the Hanford Site, Washington, USA. At these sites, Tc is present in liquid waste destined for immobilization in a waste form or has been released into the subsurface environment. The high environmental risk associated with Tc is due to its long half-life (214 000 years) and the mobility of the oxidized anionic species Tc(VII)O 4 - . Under reducing conditions, TcO 4 - is readily reduced to Tc(IV), which commonly exists as a relatively insoluble and therefore immobile, hydrous Tc-oxide (TcO 2 · n H 2 O). The stability of Tc(IV) sequestered as solid phases depends on the solubility of the solid and susceptibility to reoxidation to TcO 4 - , which in turn depend on the (biogeo)chemical conditions of the environment and/or nuclear waste streams. Unfortunately, the solubility of crystalline TcO 2 or amorphous TcO 2 ·H 2 O is still above the maximum contaminant level (MCL) established by the U.S. EPA (900 pCi/L), and the kinetics of TcO 2 oxidative dissolution can be on the order of days to years. In addition to oxygen, sulfur can form complexes that significantly affect the adsorption, solubility, and reoxidation potential of Tc, especially Tc(IV). The principal technetium sulfides are TcS 2 and Tc 2 S 7 , but much less is known about the mechanisms of formation, stabilization, and reoxidation of Tc-sulfides. A common assumption is that sulfides are less soluble than their oxyhydrous counterparts. Determination of the molecular structure of Tc 2 S 7 in particular has been hampered by the propensity of this phase to precipitate as an amorphous substance. Recent work indicates that the oxidation state of Tc in Tc 2 S 7 is Tc(IV), in apparent contradiction to its nominal stoichiometry. Technetium is relatively immobile in reduced sediments and soils, but in many cases the exact sink for Tc has not been identified. Experiments and modeling have demonstrated that both abiotic and biologic mechanisms can exert strong controls on Tc mobility and that Tc binding or uptake into sulfide phases can occur. These and similar investigations also show that extended exposure to oxidizing conditions results in transformation of sulfide-stabilized Tc(IV) to a Tc(IV)O 2 -like phase without formation of measurable dissolved TcO 4 - , suggesting a solid-state transformation in which Tc(IV)-associated sulfide is preferentially oxidized before the Tc(IV) cation. This transformation of Tc(IV)-sulfides to Tc(IV)-oxides may be the main process that limits remobilization of Tc as Tc(VII)O 4 - . The efficacy of the final waste form to retain Tc also strongly depends on the ability of oxidizing species to enter the waste and convert Tc(IV) to Tc(VII). Finally, many waste form designs are reducing (e.g., cementitious waste forms such as salt stone) and, therefore, attempt to restrict access of oxidizing species such that diffusion is the rate-limiting step in remobilization of Tc.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Unsteady heat dissipation in accelerator superconducting coils insulated with porous ceramic insulation in normal and supercritical helium conditions

To investigate the unsteady heat dissipation in accelerator superconducting coils insulated with porous ceramic insulation, two experimental mock-ups reproducing the thermal and the mechanical conditions of a superconducting coils were produced. The mock-ups with compressive load of 10 MPa and 20 MPa were tested at normal (T = 4.23 K and p = 1 bar) and supercritical helium conditions (T = 4.23 K and p = 2.0 to 3.75 bar) during unsteady heat dissipation. The paper presents the experimental results of temperature rise in both superconducting coils as a function of time for a wide range of a localized heat load varying from 0.1 kJ/m{sup 3} up to 12.8 MJ m{sup −3} per pulse. A numerical model of the transient process in these coils has been developed and the computations are compared with the experimental results.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Modelling of sawtooth-induced fast ion transport in positive and negative triangularity in TCV

Internal kinks are a common magneto hydro-dynamic (MHD) instability observed in tokamak operation when the q profile in the plasma core is close to unity. This MHD instability impacts both the transport of the bulk plasma (current, particle and energy transport) and minority species, such as fast ions. In TCV (R 0 /a = 0.88 m/0.25 m) the fast ion population is generated in the plasma by neutral beam tangential injection of energies up to 28 keV. TCV features 16 active shaping coils permitting a great flexibility in plasma shape, including negative triangularity (δ) configurations that show surprisingly high confinement. This study focuses on the transport of fast ions induced by sawteeth, by comparing two triangularity cases and simulation results with experimental data. Comparison of two equilibria with opposite δ shows that the fast ion drifts are larger for δ < 0. Furthermore, the sawtooth-induced transport in this case is larger than δ > 0 in similar conditions. Additionally, comparison with experimental data confirms the dominance of the modification of thermal kinetic profiles following the sawtooth crash in explaining drops in the neutron rates and FIDA signals. Additional fast ion diffusion, however, improves the interpretation of the experimental data. For δ < 0, the amplitude of the perturbation better representing the experimental data is larger. Finaly, an exploratory study for 50 keV particles (soon available in TCV) shows that the situation does not worsen for such particles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Grimsel Test Site - A Successful International Underground Research Laboratory for Many Decades - 20429

For more than 35 years, Nagra and its partners from around the world have been conducting underground research projects at the Grimsel Test Site (GTS, www.grimsel.com) to contribute to the development and confirmation of safe geological disposal concepts and for the characterization of suitable host rock formations. Over the years, the results of this internationally recognized research program have been, and continue to be, incorporated directly into exploration programs, modelling, safety, and engineering feasibility studies on options for deep geological repositories. Each project of the GTS program involves field-testing, laboratory studies, design and modelling tasks, and integrates all scientific and technical aspects. Each project phase is planned with a duration of three to five years to facilitate practical and administrative aspects and allow flexibility for updating the overall project plans with the latest findings. Scientific and engineering interaction among the different projects is ensured via an international steering committee meeting. Hosting an IAEA level C radiation- controlled zone, which allows use of radionuclides, including actinides such as thorium, uranium, neptunium, plutonium and americium, in in-situ experiments is one of the reasons why GTS also developed as a center of excellence for work with radioactive tracers under realistic in-situ boundary conditions. Last year, a new five-year program (2019 to 2023) started which includes projects with a planning horizon of decades. The new five-year program includes a new phase of in-situ experiments using radionuclides such as migration experiments in the Colloid Formation and Migration project (CFM), the Long-Term Diffusion experiment (LTD) and the newly established C-14 and I-129 Migration in cement project (CIM). The 'High Temperature effects on Bentonite' (HotBENT) project is starting in the current phase and is studying the effects of elevated temperatures (>175 deg. C) on bentonite materials. As a generic underground research laboratory (URL) it is expected that the GTS will provide in the coming years a platform for international collaboration, knowledge development and knowledge transfer for the next generation of scientists and engineers in the area of radioactive waste disposal and geosciences. A key role regarding knowledge transfer and training is provided by the well-established Grimsel Training Center (GTC), which (beside many URL related issues) also covers many general aspects of radioactive waste management. In this paper we provide an overview of the current program at the GTS, focusing on the experiments that study the migration of radionuclides through engineered barrier materials and the geosphere. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Model independent x-ray standing wave analysis of periodic multilayer structures

We present a model independent approach for the analysis of X-ray fluorescence yield modulated by an X-ray standing wave (XSW), that allow a fast reconstruction of the atomic distribution function inside a sample without fitting procedure. The approach is based on the direct regularized solution of the system of linear equations that characterizes the fluorescence yield. The suggested technique was optimized for, but not limited to, the analysis of periodic layered structures where the XSW is formed under Bragg conditions. The developed approach was applied to the reconstruction of the atomic distribution function for LaN/BN multilayers with 50 periods of 43 Å thick layers. The object is especially difficult to analyze with traditional methods, as the estimated thickness of the interface region between the constituent materials is comparable to the individual layer thicknesses. However, using the suggested technique, it was possible to reconstruct width of the La atomic distribution showing that the La atoms stay localized within the LaN layers and interfaces and do not diffuse into the BN layer. The analysis of the reconstructed profiles showed that the positions of the center of the atomic distribution function can be estimated with an accuracy of 1 Å.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Methane-Linked Mechanisms of Electron Uptake from Cathodes by Methanosarcina barkeri

Methanosarcinales , a lineage of cytochrome-containing methanogens, have recently been proposed to participate in direct extracellular electron transfer interactions within syntrophic communities. To shed light on this phenomenon, we applied electrochemical techniques to measure electron uptake from cathodes by Methanosarcina barkeri , which is an important model organism that is genetically tractable and utilizes a wide range of substrates for methanogenesis. Here, we confirm the ability of M. barkeri to perform electron uptake from cathodes and show that this cathodic current is linked to quantitative increases in methane production. The underlying mechanisms we identified include, but are not limited to, a recently proposed association between cathodes and methanogen-derived extracellular enzymes (e.g., hydrogenases) that can facilitate current generation through the formation of reduced and diffusible methanogenic substrates (e.g., hydrogen). However, after minimizing the contributions of such extracellular enzymes and using a mutant lacking hydrogenases, we observe a lower-potential hydrogen-independent pathway that facilitates cathodic activity coupled to methane production in M. barkeri . Our electrochemical measurements of wild-type and mutant strains point to a novel and hydrogenase-free mode of electron uptake with a potential near -484 mV versus standard hydrogen electrode (SHE) (over 100 mV more reduced than the observed hydrogenase midpoint potential under these conditions). These results suggest that M. barkeri can perform multiple modes (hydrogenase-mediated and free extracellular enzyme-independent modes) of electrode interactions on cathodes, including a mechanism pointing to a direct interaction, which has significant applied and ecological implications. IMPORTANCE Methanogenic archaea are of fundamental applied and environmental relevance. This is largely due to their activities in a wide range of anaerobic environments, generating gaseous reduced carbon that can be utilized as a fuel source. While the bioenergetics of a wide variety of methanogens have been well studied with respect to soluble substrates, a mechanistic understanding of their interaction with solid-phase redox-active compounds is limited. This work provides insight into solid-phase redox interactions in Methanosarcina spp. using electrochemical methods. We highlight a previously undescribed mode of electron uptake from cathodes that is potentially informative of direct interspecies electron transfer interactions in the Methanosarcinales .

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Relationship between the line of density anomaly and the lines of melting, crystallization, cavitation, and liquid spinodal in coarse-grained water models

Liquid water has several anomalous properties, including a non-monotonous dependence of density with temperature and an increase of thermodynamic response functions upon supercooling. Four thermodynamic scenarios have been proposed to explain the anomalies of water, but it is not yet possible to decide between them from experiments because of the crystallization and cavitation of metastable liquid water. Molecular simulations provide a versatile tool to study the anomalies and phase behavior of water, assess their agreement with the phenomenology of water under conditions accessible to experiments, and provide insight into the behavior of water in regions that are challenging to probe in the laboratory. Here we investigate the behavior of the computationally efficient monatomic water models mW and mTIP4P/2005{sup REM}, with the aim of unraveling the relationships between the lines of density extrema in the p-T plane, and the lines of melting, liquid-vapor spinodal and non-equilibrium crystallization and cavitation. We focus particularly on the conditions for which the line of density maxima (LDM) in the liquid emerges and disappears as the pressure is increased. We find that these models present a retracing LDM, same as previously found for atomistic water models and models of other tetrahedral liquids. The low-pressure end of the LDM occurs near the pressure of maximum of the melting line, a feature that seems to be general to models that produce tetrahedrally coordinated crystals. We find that the mW water model qualitatively reproduces several key properties of real water: (i) the LDM is terminated by cavitation at low pressures and by crystallization of ice I{sub h} at high pressures, (ii) the LDM meets the crystallization line close to the crossover in crystallization from ice I{sub h} to a non-tetrahedral four-coordinated crystal, and (iii) the density of the liquid at the crossover in crystallization from ice I{sub h} to a four-coordinated non-tetrahedral crystal coincides with the locus of maximum in diffusivity as a function of pressure. The similarities in equilibrium and non-equilibrium phase behavior between the mW model and real water provide support to the quest to find a compressibility extremum, and determine whether it presents a maximum, in the doubly metastable region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

High frequency impedance characteristics of a tunable microplasma device

Computational studies on high frequency impedance characteristics of a microplasma device are reported. While microplasma is ignited using a primary excitation signal, frequency response of plasma impedance is determined by a secondary high frequency probe signal with significantly lower voltage amplitude such that it does not influence the plasma parameters. Here, the computational model utilizing the drift–diffusion approximation is first validated by comparing with experimental data for microplasmas ignited at pressures ranging from 1 to 5 Torr. In spite of quantitative discrepancies, good overall agreement is obtained between the measured frequency response of impedance of the discharge. Comparisons are also presented for various plasma parameters including mean electron number density, sheath thickness, mean electron temperature, and collision frequency that were inferred from the impedance measurements. The computational model is then used to perform simulations of near-atmospheric pressure microplasmas with the probe signal frequency ranging from 3 to 20 GHz. The simulations demonstrate the presence of a resonance frequency at which the impedance vanishes. More importantly, it is shown that this resonant frequency can be tuned effectively by suitably modifying the operating parameters (gap size, pressure, and excitation voltage). The simulated impedance characteristics are used to determine the effective plasma inductance and capacitance using a non-linear fitting approach, thereby showing the dependence of these electrical parameters on the plasma operating conditions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Understanding and Tailoring Diffusion and Co-Adsorption Inside the Confined Pores of Metal-Organic Frameworks (Final Scientific/Technical Report for Award DE-SC0019902)

The aim of this program was to gain a fundamental understanding of the behavior of various guest molecules in nano-confined environments, such as metal organic frameworks (MOFs), using a combination of novel synthesis, ab initio modeling, and in situ characterization. Through this project, we developed a concise understanding of the mechanisms that control adsorption/desorption of gaseous molecules and their mixtures, leading to design/synthesis guidelines for MOFs with desired functionality. We further developed methods to disentangle kinetic from thermodynamic effects during adsorption, as well as to characterize the interactions at play. In the first funding cycle, the focus was on the unambiguously characterization of co-adsorption and diffusion of gasses/vapors and their mixtures. In the second funding cycle, the focus was on characterizing the effects of the nano-confinement on the kinetics and thermodynamics of adsorption processes inside MOFs, again with an emphasis on mixtures of gasses and vapors. The nano-confinement can tip the thermodynamic vs. kinetic balance, and current understanding and theory based on single-component analysis can lead to incorrect predictions for mixtures. This is of particular interest in real-world applications, where gasses/vapors are typically mixed, contain impurities, or are often exposed to humid conditions. Our main findings were: (i) within confined environments the adsorption behavior of mixed gasses/vapors can be drastically different from the “sum” of the corresponding single phases; (ii) co-adsorption is often competitive and detrimental to performance, but it can also be cooperative and beneficial; (iii) in some co-adsorbed gasses/vapors, molecules that are strongly bound in the single-component phase can be replaced by molecules that are nominally weaker bound (molecular exchange) due to guest-guest interactions that lower the kinetic barriers and favor the final adsorption state; (iv) kinetic and thermodynamic effects can be precisely controlled through pore-size engineering and synthesis; and, (v) kinetic effects can be identified and disentangled from thermodynamic effects during adsorption through a series of sequential and simultaneous gas loading measurements. The short-term goal of this program was the controlling and understanding of common MOF systems in real-world situations where gasses/vapors are mixed, which will have an important impact on industrial processes and applications from gas storage and sequestration to catalysis and sensors. The long-term goals include the development of theoretical and experimental methods for gaining a fundamental understanding of adsorption/reaction processes within MOFs, as well as new guidelines for synthesizing MOFs with tailored physical and chemical properties.

36 MATERIALS SCIENCE↗