Results for “Alternating minimization” — Page 18

DOE OSTI2014

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistry of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO 2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO 2 . Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Cross-plane coherent acoustic phonons in two-dimensional organic-inorganic hybrid perovskites

Two-dimensional, Ruddlesden-Popper organic-inorganic hybrid layered perovskites (2D-RPs) are solution-grown semiconductors with prospective applications in next-generation optoelectronics. The heat-carrying, low-energy acoustic vibrations of 2D-RPs, which are important for heat management of 2D-RP-based devices, have remained unexplored. Here we report on the propagation of coherent longitudinal acoustic phonons along the cross-plane direction of 2D-RPs, following separate characterizations of below-bandgap refractive index for each 2D-RP. Through experiments on crystals of systematically varied perovskite layer thickness, we demonstrate significant reduction in both group velocity and propagation length of acoustic phonons in 2D-RPs as compared to the three-dimensional methylammonium lead iodide. As borne out by a minimal coarse-grained model, these vibrational properties arise from a large acoustic impedance mismatch between the alternating layers of perovskite sheets and bulky organic cations. Furthermore, our results inform on thermal transport in highly impedance-mismatched crystal sub-lattices and provide insights towards design of materials that exhibit highly anisotropic thermal dissipation properties.

36 MATERIALS SCIENCE↗

DOE OSTI2021

An orthogonal metabolic framework for one-carbon utilization

Metabolic engineering often entails concurrent engineering of substrate utilization, central metabolism, and product synthesis pathways to maximize the conversion of a carbon substrate into desired product(s). Here, we report an alternative approach using synthetic pathways for C1 bioconversion that are orthogonal to the host metabolic network, thus minimizing interdependency on native metabolism and enabling more efficient biocatalysts. Here, the engineered pathways are based on formyl-CoA elongation (FORCE) reactions catalyzed by the enzyme 2-hydroxyacyl-CoA lyase (HACL) and generate multi-carbon products directly from C1 elongation units in the form of formyl-CoA. Herein, we use thermodynamic and stoichiometric analyses to evaluate different FORCE pathway variants, including aldose elongation, α-reduction, and aldehyde elongation. Promising variants were further prototyped using cell-free systems (purified enzymes and cell extracts) as well as resting and growing cultures of non-methylotrophic bacterium Escherichia coli. We demonstrate that C1 substrates formate, formaldehyde, and methanol can be used as inputs for FORCE pathways and that FORCE reactions can serve as a platform for varied product synthesis including glycolate, ethylene glycol, ethanol, and glycerate. Furthermore, the orthogonal FORCE pathways have the potential to be integrated with host metabolism for synthetic methylotrophy by the production of native growth substrates as demonstrated in a two-strain culture system.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2014

Deriving the Hirshfeld partitioning using distance metrics

The atoms in molecules associated with the Hirshfeld partitioning minimize the generalized Hellinger-Bhattacharya distance to the reference pro-atom densities. Moreover, the reference pro-atoms can be chosen by minimizing the distance between the pro-molecule density and the true molecular density. This provides an alternative to both the heuristic “stockholder” and the mathematical information-theoretic interpretations of the Hirshfeld partitioning. These results extend to any member of the family of f-divergences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Spectral distortions of the CMB dipole

We consider the distortions of the cosmic microwave background (CMB) dipole anisotropy related to primordial recombination radiation (PRR) and primordial y- and μ-distortions. The signals arise due to our motion relative to the CMB restframe and appear as a frequency-dependent distortion of the CMB temperature dipole. To leading order, the expected relative distortion of the CMB dipole does not depend on the particular observation directions and reaches the level of 10{sup −6} for the PRR- and μ-distortions and 10{sup −5} for the y-distortion in the frequency range 1–700 GHz. The temperature differences arising from the dipole anisotropy of the relic CMB distortions depend on the observation directions. For mutually opposite directions, collinear to the CMB dipole axis, the temperature differences due to the PRR- and μ-dipole anisotropy attain values ΔT≃10 nK in the considered range. The temperature difference arising from the y-dipole anisotropy may reach values of up to 1 μK. The key features of the considered effect are as follow: (i) an observation of the effect does not require absolute calibration; (ii) patches of sky with minimal foreground contamination can be chosen. Future measurements of the CMB dipole distortion thus will provide an alternative method for direct detection of the PRR-, y-, and μ-distortions. The y-distortion dipole may be detectable with PIXIE at a few standard deviations.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Data-Based Resilience Enhancement Strategies for Electric-Gas Systems Against Sequential Extreme Weather Events

Some extreme weather events, such as the hurricane, pass through an area sequentially and thus are called sequential extreme weather events (SEWEs). This paper proposes a data-based robust optimization (RO) model to enhance the resilience of the integrated electricity and gas system (IEGS) against SEWEs. Specifically, the SEWE strikes the IEGS sequentially. After each attack, the system state is adjusted immediately to minimize the maximized expected system cost caused by the SEWE. The attack-defense procedures are repeated alternatively during the SEWE. Preventive measures, hardening, are made in advance to reduce the impact of sequential attacks. The entire process is formulated as a multi-period RO model. Furthermore, it is proved that the most effective resilience enhancement strategies for this model are the same as those for a two-stage RO model, which can be solved by the nested column-and-constraint generation (C&CG) algorithm. In addition, the property of SEWEs, sequentially endangering limited regions of the IEGS, is incorporated to build a data-based uncertainty set and reduce its conservativeness. Simulation results on two IEGSs validate the effectiveness of the proposed model.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2018

Self-Organization of Phase Clusters in Homogeneously Disordered Polymer Composite Materials

The surface morphologies of homogeneously disordered polymer composite films and coatings prepared using mixtures of components with limited or negligible mutual solubility are studied by electron microscopy. We elaborate on the characteristic self-organization of phase clusters in our samples, in which one phase gives rise to the structural scaffold of the composite, an internal percolation cluster of particles. The cluster cavities filled with discrete particle aggregates of the other phase are characterized by a relatively narrow Gaussian-like size distribution. This topological structure arises if composites are prepared by observing specific concentration conditions or using structure modifiers that affect particle aggregation. Self-organization of phase clusters minimizes the entropy production when the components are mixed and gives rise to local ordering in spatial alternation of particle aggregates. The local order transforms into cellular disorder as the length scale increases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

An ensemble model of QSAR tools for regulatory risk assessment

Quantitative structure activity relationships (QSARs) are theoretical models that relate a quantitative measure of chemical structure to a physical property or a biological effect. QSAR predictions can be used for chemical risk assessment for protection of human and environmental health, which makes them interesting to regulators, especially in the absence of experimental data. For compatibility with regulatory use, QSAR models should be transparent, reproducible and optimized to minimize the number of false negatives. In silico QSAR tools are gaining wide acceptance as a faster alternative to otherwise time-consuming clinical and animal testing methods. However, different QSAR tools often make conflicting predictions for a given chemical and may also vary in their predictive performance across different chemical datasets. In a regulatory context, conflicting predictions raise interpretation, validation and adequacy concerns. To address these concerns, ensemble learning techniques in the machine learning paradigm can be used to integrate predictions from multiple tools. By leveraging various underlying QSAR algorithms and training datasets, the resulting consensus prediction should yield better overall predictive ability. We present a novel ensemble QSAR model using Bayesian classification. The model allows for varying a cut-off parameter that allows for a selection in the desirable trade-off between model sensitivity and specificity. The predictive performance of the ensemble model is compared with four in silico tools (Toxtree, Lazar, OECD Toolbox, and Danish QSAR) to predict carcinogenicity for a dataset of air toxins (332 chemicals) and a subset of the gold carcinogenic potency database (480 chemicals). Leave-one-out cross validation results show that the ensemble model achieves the best trade-off between sensitivity and specificity (accuracy: 83.8 % and 80.4 %, and balanced accuracy: 80.6 % and 80.8 %) and highest inter-rater agreement [kappa (κ): 0.63 and 0.62] for both the datasets. The ROC curves demonstrate the utility of the cut-off feature in the predictive ability of the ensemble model. In conclusion, this feature provides an additional control to the regulators in grading a chemical based on the severity of the toxic endpoint under study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

The Effect of Rolling As-Cast and Homogenized U-10Mo Samples on the Microstructure Development and Recovery Curves

Over the past several years Pacific Northwest National Laboratory (PNNL) has been actively involved in supporting the U.S. Department of Energy National Nuclear Security Administration Office of Material Management and Minimization (formerly Global Threat Reduction Initiative). The U.S. High-Power Research Reactor (USHPRR) project is developing alternatives to existing highly enriched uranium alloy fuel to reduce the proliferation threat. One option for a high-density metal fuel is uranium alloyed with 10 wt% molybdenum (U-10Mo). Forming the U-10Mo fuel plates/foils via rolling is an effective technique and is actively being pursued as part of the baseline manufacturing process. The processing of these fuel plates requires systematic investigation/understanding of the pre- and post-rolling microstructure, end-state mechanical properties, residual stresses, and defects, their effect on the mill during processing, and eventually, their in-reactor performance. In the work documented herein, studies were conducted to determine the effect of cold and hot rolling the as-cast and homogenized U-10Mo on its microstructure and hardness. The samples were homogenized at 900°C for 48 h, then later annealed for several durations and temperatures to investigate the effect on the material’s microstructure and hardness. The rolling of the as-cast plate, both hot and cold, was observed to form a molybdenum-rich and -lean banded structure. The cold rolling was ineffective, and in some cases exacerbated the as-cast defects. The grains elongated along the rolling direction and formed a pancake shape, while the carbides fractured perpendicularly to the rolling direction and left porosity between fractured particles of UC. The subsequent annealing of these samples at sub-eutectoid temperatures led to rapid precipitation of the α + γ ' lamellar phase, mainly in the molybdenum-lean regions. Annealing the samples above the eutectoid temperature did not refine the grain size or the banded microstructure. However, annealing the samples led to quick recovery in hardness as evidenced by a drop in Vickers hardness of 20%. Hot rolling was performed at 650 and 800°C. The hot-rolling mill loads (load separation force) were approximately 40 to 50% less than the cold-rolling for the same reduction and thickness. It was observed that hot rolling the samples with 50% or more reduction in thickness were responsible for dynamic recrystallization in the hot-rolled samples and led to grain refinement. Unlike the cold-rolled samples, the hot-rolled samples did not fracture the carbides and appeared to heal the casting defects. The recovery phenomenon was similar to the cold-rolled samples above the eutectoid temperatures, but owing to the refined grain size, the precipitation of the lamellar phase was far more rapid in these samples and the hardness increased more rapidly than in the cold rolled sample when heated below the eutectoid temperature. The data generated from these rolling efforts has been used to make the process modeling efforts more robust and applicable to all USHPRR partner rolling mills. The flow stress for cold rolling the samples was determined to be between 170-190 ksi, with frictional forces between 0.2 and 0.4 for the PNNL mill. The measured roll separation forces and those simulated using finite element methods for hot and cold rolling for the PNNL rolling mill were in good agreement.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2015

Label Free Detection of L-Glutamate Using Microfluidic Based Thermal Biosensor

A thermoelectric biosensor for the detection of L-glutamate concentration was developed. The thermoelectric sensor is integrated into a micro-calorimeter which measures the heat produced by biochemical reactions. The device contains a single flow channel that is 120 µm high and 10 mm wide with two fluid inlets and one fluid outlet. An antimony-bismuth (Sb-Bi) thermopile with high common mode rejection ratio is attached to the lower channel wall and measures the dynamic changes in the temperature when L-glutamate undergoes oxidative deamination in the presence of glutamate oxidase (GLOD). The thermopile has a Seebeck coefficient of ~7 µV·(m·K)-1 . The device geometry, together with hydrodynamic focusing, eliminates the need of extensive temperature control. Layer-by-layer assembly is used to immobilize GLOD on the surface of glass coverslips by alternate electrostatic adsorption of polyelectrolyte and GLOD. The impulse injection mode using a 6-port injection valve minimizes sample volume to 5 µL. The sensitivity of the sensor for glutamate is 17.9 nVs·mM-1 in the linear range of 0–54 mM with an R2 value of 0.9873. The lowest detection limit of the sensor for glutamate is 5.3 mM.

layer-by-layer self-assembly↗

DOE OSTI2025

Supporting Information - How Can Crop Production Adapt to growing groundwater restrictions in the West?

Abstract This data plan outlines the structure and content of datasets generated and utilized in the research presented in the manuscript abstract. Groundwater overdraft has led to serious water supply issues in the US West. Most western states manage groundwater use through a permitting system, but California has only recently begun to restrict groundwater use statewide with the 2014 passage of groundwater restrictions which target the elimination of groundwater overdraft practices by 2042. With groundwater extraction curtailed, crop production in the US West (a $95 billion industry annually) will be affected, and appropriate response strategies will be needed to ensure minimal disruption to food production and the regional economy. In this paper, we explore the adoption of alternative adaptive responses: (a) deficit irrigation; (b) switching to less water-intensive crops; (c) changing the extent of irrigated land (including fallowing); and (d) geographically shifting crop production. Employing an integrated modeling approach, we explicitly capture the interactions and feedbacks between local hydrology, changes in crop yields, crop and land use decision-making, changes in crop prices, and regional shifts in crop production. We find that the optimal adaptive response is spatially heterogeneous and comprises a portfolio of strategies. Southwestern states and California will be the most impacted by groundwater restrictions. The optimal responses in these states are to both adopt deficit irrigation strategies and reduce a portion of their irrigated croplands, resulting in a shift in crop production to northwestern states with a larger supply of water. The datasets detailed in this repository represent the output from these integrated models, specifically designed to support the analysis and visualization presented in the manuscript and supplemental information. These datasets, used in conjunction with the scripts available at our associated GitHub repository (https://github.com/pches/Femeena_etal_How_can_crop_production_adapt), enable the reproduction of figures and facilitate a comprehensive understanding of the optimal adaptive strategies in agriculture for mitigating water stress under varying groundwater extraction scenarios, as outlined in the abstract.

DNDCe↗

DOE OSTI2025

Supporting Information - How Can Crop Production Adapt to growing groundwater restrictions in the West?

Abstract This data plan outlines the structure and content of datasets generated and utilized in the research presented in the manuscript abstract. Groundwater overdraft has led to serious water supply issues in the US West. Most western states manage groundwater use through a permitting system, but California has only recently begun to restrict groundwater use statewide with the 2014 passage of groundwater restrictions which target the elimination of groundwater overdraft practices by 2042. With groundwater extraction curtailed, crop production in the US West (a $95 billion industry annually) will be affected, and appropriate response strategies will be needed to ensure minimal disruption to food production and the regional economy. In this paper, we explore the adoption of alternative adaptive responses: (a) deficit irrigation; (b) switching to less water-intensive crops; (c) changing the extent of irrigated land (including fallowing); and (d) geographically shifting crop production. Employing an integrated modeling approach, we explicitly capture the interactions and feedbacks between local hydrology, changes in crop yields, crop and land use decision-making, changes in crop prices, and regional shifts in crop production. We find that the optimal adaptive response is spatially heterogeneous and comprises a portfolio of strategies. Southwestern states and California will be the most impacted by groundwater restrictions. The optimal responses in these states are to both adopt deficit irrigation strategies and reduce a portion of their irrigated croplands, resulting in a shift in crop production to northwestern states with a larger supply of water. The datasets detailed in this repository represent the output from these integrated models, specifically designed to support the analysis and visualization presented in the manuscript and supplemental information. These datasets, used in conjunction with the scripts available at our associated GitHub repository (https://github.com/pches/Femeena_etal_How_can_crop_production_adapt), enable the reproduction of figures and facilitate a comprehensive understanding of the optimal adaptive strategies in agriculture for mitigating water stress under varying groundwater extraction scenarios, as outlined in the abstract.

DNDCe↗

DOE OSTI2025

Supporting Information - How Can Crop Production Adapt to growing groundwater restrictions in the West?

Abstract This data plan outlines the structure and content of datasets generated and utilized in the research presented in the manuscript abstract. Groundwater overdraft has led to serious water supply issues in the US West. Most western states manage groundwater use through a permitting system, but California has only recently begun to restrict groundwater use statewide with the 2014 passage of groundwater restrictions which target the elimination of groundwater overdraft practices by 2042. With groundwater extraction curtailed, crop production in the US West (a $95 billion industry annually) will be affected, and appropriate response strategies will be needed to ensure minimal disruption to food production and the regional economy. In this paper, we explore the adoption of alternative adaptive responses: (a) deficit irrigation; (b) switching to less water-intensive crops; (c) changing the extent of irrigated land (including fallowing); and (d) geographically shifting crop production. Employing an integrated modeling approach, we explicitly capture the interactions and feedbacks between local hydrology, changes in crop yields, crop and land use decision-making, changes in crop prices, and regional shifts in crop production. We find that the optimal adaptive response is spatially heterogeneous and comprises a portfolio of strategies. Southwestern states and California will be the most impacted by groundwater restrictions. The optimal responses in these states are to both adopt deficit irrigation strategies and reduce a portion of their irrigated croplands, resulting in a shift in crop production to northwestern states with a larger supply of water. The datasets detailed in this repository represent the output from these integrated models, specifically designed to support the analysis and visualization presented in the manuscript and supplemental information. These datasets, used in conjunction with the scripts available at our associated GitHub repository (https://github.com/pches/Femeena_etal_How_can_crop_production_adapt), enable the reproduction of figures and facilitate a comprehensive understanding of the optimal adaptive strategies in agriculture for mitigating water stress under varying groundwater extraction scenarios, as outlined in the abstract.

DNDCe↗

NASA NTRS1985

On the geodetic applications of simultaneous range differences to Lageos

While the majority of the currently deployed satellite laser systems are of centimeter level precision, the accuracy of the geodetic products corresponds to the accuracy in which geodesists are interested. On several occasions, the best models are either not good enough or result in tedious computations which are required to achieve accuracies comparable to those of the observations. A possible alternative is related to the development of a new method of data analysis. This method involves the minimization of the effect of the systematic errors and, in particular, the minimization of errors arising from an incorrectly modeled orbit. The present paper provides a summary of the results of a study of this option, taking into account laser ranging data from Lageos.

Pavlis, E. C.↗

NASA NTRS1991

Spatial adaption procedures on unstructured meshes for accurate unsteady aerodynamic flow computation

Spatial adaption procedures for the accurate and efficient solution of steady and unsteady inviscid flow problems are described. The adaption procedures were developed and implemented within a two-dimensional unstructured-grid upwind-type Euler code. These procedures involve mesh enrichment and mesh coarsening to either add points in a high gradient region or the flow or remove points where they are not needed, respectively, to produce solutions of high spatial accuracy at minimal computational costs. A detailed description is given of the enrichment and coarsening procedures and comparisons with alternative results and experimental data are presented to provide an assessment of the accuracy and efficiency of the capability. Steady and unsteady transonic results, obtained using spatial adaption for the NACA 0012 airfoil, are shown to be of high spatial accuracy, primarily in that the shock waves are very sharply captured. The results were obtained with a computational savings of a factor of approximately fifty-three for a steady case and as much as twenty-five for the unsteady cases.

Rausch, Russ D.↗

NASA NTRS2003

Base Passive Porosity for Vehicle Drag Reduction

A device for controlling drag on a ground vehicle. The device consists of a porous skin or skins mounted on the trailing surface and/or aft portions of the ground vehicle. The porous skin is separated from the vehicle surface by a distance of at least the thickness of the porous skin. Alternately, the trailing surface, sides, and/or top surfaces of the ground vehicle may be porous. The device minimizes the strength of the separation in the base and wake regions of the ground vehicle, thus reducing drag.

Bauer, Steven X. S.↗

NASA NTRS1993

Characteristics of Ferromagnetic Flux Focusing Lens in the Development of Surface/Subsurface Flaw Detector

Electromagnetic NDE techniques have in the past steered away from the use of ferromagnetic materials. Although their high permeabilities lead to increased field levels, the properties of ferrous elements in the presence of alternating magnetic fields are difficult to determine. In addition, their use leads to losses which can be minimized through the use of low conductivity ferrites. In fact, the eddy current probes which do incorporate ferromagnetic materials have focused on these losses and the shielding which can be obtained by surrounding a probe with a high permeability, conducting material. Eddy current probes enclosed in conducting and magnetic shields have been used to prevent the generated fields from interacting with materials in the vicinity of the probe, such as when testing near material boundaries. A recent invention has used ferromagnetic shielding to magnetically separate individual concentric eddy current probes in order to eliminate cross-talk between the probes so that simultaneous detection of different types of flaws at different depths can be achieved. In contrast to the previous uses of ferromagnetic materials purely as magnetic shields, an electromagnetic flaw detector recently developed at NASA Langley Research Center takes advantage of the flux focusing properties of a ferromagnetic mild steel in order to produce a simple, effective device for the non-destructive evaluation of conducting materials. The Flux Focusing Eddy Current Probe has been shown to accurately measure material thickness and fatigue damage. The straight forward flaw response of the probe makes the device ideal for rapid inspection of large structures, and has lead to its incorporation in a computer controlled search routine to locate fatigue crack tips and monitor experimental fatigue crack growth experiments.

Wincheski, Buzz↗

NASA NTRS2003

Base passive porosity for vehicle drag reduction

A device for controlling drag on a ground vehicle. The device consists of a porous skin or skins mounted on the trailing surface and/or aft portions of the ground vehicle. The porous skin is separated from the vehicle surface by a distance of at least the thickness of the porous skin. Alternately, the trailing surface, sides, and/or top surfaces of the ground vehicle may be porous. The device minimizes the strength of the separation in the base and wake regions of the ground vehicle, thus reducing drag.

Bauer, Steven X. S.↗