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At least 1,243 records · Page 69

Leaf water potential measurements using the pressure chamber: Synthetic testing of assumptions towards best practices for precision and accuracy

Leaf water potential (ψ leaf ), typically measured using the pressure chamber, is the most important metric of plant water status, providing high theoretical value and information content for multiple applications in quantifying critical physiological processes including drought responses. Pressure chamber measurements of ψ leaf (ψ leafPC ) are most typical, yet, the practical complexity of the technique and of the underlying theory has led to ambiguous understanding of the conditions to optimize measurements. Consequently, specific techniques and precautions diversified across the global research community, raising questions of reliability and repeatability. Here, we surveyed specific methods of ψ leafPC from multiple laboratories, and synthesized experiments testing common assumptions and practices in ψ leafPC for diverse species: (i) the need for equilibration of previously transpiring leaves; (ii) leaf storage before measurement; (iii) the equilibration of ψ leaf for leaves on bagged branches of a range of dehydration; (iv) the equilibration of ψ leaf across the lamina for bagged leaves, and the accuracy of measuring leaves with artificially ‘elongated petioles’; (v) the need in ψ leaf measurements for bagging leaves and high humidity within the chamber; (vi) the need to avoid liquid water on leaf surfaces; (vii) the use of ‘pulse’ pressurization versus gradual pressurization; and (viii) variation among experimenters in ψ leafPC determination. Based on our findings we provide a best practice protocol to maximise accuracy, and provide recommendations for ongoing species-specific tests of important assumptions in future studies.

54 ENVIRONMENTAL SCIENCES↗

LANL Contributions to pyiron: An integrated development environment for computational materials science

To support and accelerate the development of simulation protocols in atomistic modelling, we introduce an integrated development environment (IDE) for computational materials science called pyiron (http://pyiron.org). The pyiron IDE combines a web based source code editor, a job management system for build automation, and a hierarchical data management solution. The core components of the pyiron IDE are pyiron objects based on an abstract class, which links application structures such as atomistic structures, projects, jobs, simulation protocols and computing resources with persistent storage and an interactive user environment. The simulation protocols within the pyiron IDE are constructed using the Python programming language. To highlight key concepts of this tool as well as to demonstrate its ability to simplify the implementation and testing of simulation protocols we discuss two applications. In these examples we show how pyiron supports the whole life cycle of a typical simulation, seamlessly combines ab initio with empirical potential calculations, and how complex feedback loops can be implemented. While originally developed with focus on ab initio thermodynamics simulations, the concepts and implementation of pyiron are general thus allowing to employ it for a wide range of simulation topics.

Janssen, Jan↗

Fiber optic-based biosensor

The NRL fiber optic biosensor is a device which measures the formation of a fluorescent complex at the surface of an optical fiber. Antibodies and DNA binding proteins provide the mechanism for recognizing an analyze and immobilizing a fluorescent complex on the fiber surface. The fiber optic biosensor is fast, sensitive, and permits analysis of hazardous materials remote from the instrumentation. The fiber optic biosensor is described in terms of the device configuration, chemistry for protein immobilization, and assay development. A lab version is being used for assay development and performance characterization while a portable device is under development. Antibodies coated on the fiber are stable for up to two years of storage prior to use. The fiber optic biosensor was used to measure concentration of toxins in the parts per billion (ng/ml) range in under a minute. Immunoassays for small molecules and whole bacteria are under development. Assays using DNA probes as the detection element can also be used with the fiber optic sensor, which is currently being developed to detect biological warfare agents, explosives, pathogens, and toxic materials which pollute the environment.

Ligler, Frances S.↗

NMR Relaxometry and Diffusometry Analysis of Dynamics in Ionic Liquids and Ionogels for Use in Lithium-Ion Batteries

Solvation and transport properties of methlyviologen dichloride in mixtures of choline chloride (ChCl) and ethylene glycol (EG) including the deep eutectic solvent (DES) ethaline were studied through physical property measurements, cyclic voltammetry, and Raman spectroscopy. The transport properties of the solvate structures in ethaline and ChCl:EG mixtures were compared to a well-studied ionic liquid (IL), 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [PYR13][TFSI] through the lens of hole theory. Exchanging the chloride anion of ethaline with bis(trifuoromethylsufonyl)imide) anion, [TFSI], is found to increase the fluidity of the solvent and promoted stronger solute-solvent interactions. Raman spectroscopy shows that methylviologen is solvated by EG in solutions with ChTFSI but interstitially accommodated in void spaces in both ChCl solutions and [PYR13][TFSI]. Complex solvents such as DESs are regarded as “designer solvents” and we demonstrate that the physical properties and solvation characteristics of these fluids can be varied by anion exchange of hydrogen bond acceptors.

25 ENERGY STORAGE↗

Atomic-scale probing of short-range order and its impact on electrochemical properties in cation-disordered oxide cathodes

Abstract Chemical short-range-order has been widely noticed to dictate the electrochemical properties of Li-excess cation-disordered rocksalt oxides, a class of cathode based on earth abundant elements for next-generation high-energy-density batteries. Existence of short-range-order is normally evidenced by a diffused intensity pattern in reciprocal space, however, derivation of local atomic arrangements of short-range-order in real space is hardly possible. Here, by a combination of aberration-corrected scanning transmission electron microscopy, electron diffraction, and cluster-expansion Monte Carlo simulations, we reveal the short-range-order is a convolution of three basic types: tetrahedron, octahedron, and cube. We discover that short-range-order directly correlates with Li percolation channels, which correspondingly affects Li transport behavior. We further demonstrate that short-range-order can be effectively manipulated by anion doping or post-synthesis thermal treatment, creating new avenues for tailoring the electrochemical properties. Our results provide fundamental insights for decoding the complex relationship between local chemical ordering and properties of crystalline compounds.

25 ENERGY STORAGE↗

Bismuth Electrocatalyst Enabling Reversible Redox Kinetics of a Chelated Chromium Flow Battery Anolyte

Metal electrocatalysts have been reported to improve the electron transfer kinetics of aqueous redox flow battery electrolytes on various types of carbon electrodes. In this work, we electrodeposited bismuth metal onto a carbon paper anode of a redox flow battery containing our previously reported polyaminocarboxylate-chelated chromium electrolyte. Depositing 0.58 mg cm –2 of bismuth metal enabled an electrochemically reversible electron transfer for the Cr(II)/Cr(III) couple, resulting in a 3.9% voltage efficiency increase over ten cycles at 100 mA cm –2 across an 80% state of charge window, while maintaining >99% current efficiency. The bismuth electrocatalyst provided other improvements, such as a 13% increase in average discharge power density when cycling at 80% energy efficiency, along with a 60% decrease in charge transfer resistance and 12% decrease in the full cell area specific resistance. A chelated bismuth complex was also utilized as a bismuth source for electrodeposition, providing an example of how polyaminocarboxylate ligands can be further implemented into efforts towards improving the energy efficiency of aqueous redox flow batteries.

25 ENERGY STORAGE↗

Identification of Solid-Electrolyte Interphase Species by Joint Characterization of Li-Ion Battery Chemistry by Mass Spectrometry and Electrochemical Reaction Networks

The formation and stability of the solid-electrolyte interphase (SEI) play central roles in determining the long-term performance and safety of modern electrochemical energy storage systems. Despite decades of research, the SEI’s heterogeneous, dynamic, and multiphase nature has defied comprehensive molecular-level characterization, creating a critical knowledge gap that limits rational battery design. In this work, we introduce a computational−experimental framework that integrates high-throughput quantum chemistry calculations, data-driven electrochemical reaction networks (eCRNs), stochastic algorithms, and laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (LDI-FTICR-MS) to unravel SEI formation in carbonatebased electrolytes without imposing predefined mechanisms. We constructed the most comprehensive eCRN to date, spanning over 10,000 species and 209 million reactions. Through stochastic network analysis, we successfully recovered 27 species that were previously reported in the literature and predicted 28 novel SEI species nearly doubling our scientific knowledge in this area. Each new species was rigorously confirmed through advanced mass spectral analysis of its distinct molecular and isotopic signatures. We kinetically refined the formation pathways for a select set of both previously reported and novel SEI products, revealing kinetically feasible elementary reaction mechanisms with activation barriers below 1 eV. This computational−experimental approach deepens our molecular-level understanding of SEI chemistry by resolving which species form and through which decomposition mechanisms they emerge. Such knowledge provides the foundation necessary to connect electrolyte composition to the resulting SEI components, a critical step toward a more informed electrolyte development in next-generation lithium-based batteries.

25 ENERGY STORAGE↗

Analysis of degradation in residential battery energy storage systems for rate-based use-cases

This article examines the impact of residential battery energy storage (BES) systems' operational modes on the life (i.e. usable energy capacity) of the battery under several climatic conditions and battery chemistries. The sharp increase in residential BES installations has been a result of decreasing costs of batteries, increase in rate structures motivated applications such as solar self-consumption and time-of-use energy management, and customers purchasing these systems for backup power. While these different modes of operations provide a combination of increased bill savings, reliability of supply, and energy sustainability to the customer, their operational characteristics vary significantly between use-cases. Functional life of BES systems is known to be strongly dependent on their operating conditions. In this article, we analyze the operation of residential BES systems under different rate-based use-cases, for different battery chemistries and cell designs, and under different environmental conditions. This is conducted by simulating the control of BES operations using rate-based cycling algorithms and analyzing the prognosis of multiple battery lifetime models that consider complex nonlinear dependencies of operational stress factors such as state-of-charge, depth-of-discharge, and temperature on degradation. Significant variations in battery life are observed owing to the differences in characteristics of the uses-cases coupled with environmental conditions and battery chemistries. Such differences lead to the conclusion that choice of residential BES technologies and chemistries should account for their intended use-cases.

25 ENERGY STORAGE↗

Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

25 ENERGY STORAGE↗

Coastal Wetland Carbon Processes in a Warmer Climate (Final Report)

Coastal wetlands are global hotspots of carbon storage. Marshes, mangroves, and seagrass meadows account for about half of the total marine soil carbon budget and bury carbon at rates roughly equivalent to terrestrial forests despite occupying just 2.5% of Earth’s land area. Coastal wetlands have recently been recognized as important for storing carbon, but the future sink strength and carbon stock stability of these systems is uncertain because global change drivers such as temperature and elevated CO 2 disturb the complex ecology that drives high rates of soil carbon sequestration. The dynamics of coastal wetland carbon pools are not presently represented in earth system models. Our goals are to understand the influence of warming and elevated CO 2 on C cycling and to forecast the stability of tidal wetland soil carbon pools at the terrestrial-aquatic interface. We designed and implemented a novel field manipulation of elevated CO 2 and temperature and operated it from 2016 to 2020. We learned that plant communities and microbial communities respond differently to rising temperature, and that the net effects of these responses means that a modest amount of warming will increase tidal marsh carbon sequestration, while warming above that level will diminish the potential for additional carbon sequestration. In mathematical terms the system showed non-linear responses which are important for building forecast models.

54 ENVIRONMENTAL SCIENCES↗

Theoretical and Experimental Flow Cell Studies of a Hydrogen-Bromine Fuel Cell, Part 1

There is increasing interest in hydrogen-bromine fuel cells as both primary and regenerative energy storage systems. One promising design for a hydrogen-bromine fuel cell is a negative half cell having only a gas phase, which is separated by a cationic exchange membrane from a positive half cell having an aqueous electrolyte. The hydrogen gas and the aqueous bromide solution are stored external to the cell. In order to calculate the energy storage capacity and to predict and assess the performance of a single cell, the open circuit potential (OCV) must be estimated for different states of change, under various conditions. Theoretical expressions were derived to estimate the OCV of a hydrogen-bromine fuel cell. In these expressions temperature, hydrogen pressure, and bromine and hydrobromic acid concentrations were taken into consideration. Also included are the effects of the Nafion membrance separator and the various bromide complex species. Activity coefficients were taken into account in one of the expressions. The sensitivity of these parameters on the calculated OCV was studied.

Savinell, R. F.↗

Overview of Additively Manufactured TPS Proposed Flight Test and Earth Re-Entry Capsule Design

A flight mechanics overview is presented of an Earth flight test designed to investigate a novel, 3D printed thermal protection system (TPS) that is currently in development at NASA as part of the Additive Manufacturing of Thermal Protection Systems project. The project is pioneering a method to print a thermal protection system onto an entry vehicle forebody one layer at a time. This method reduces labor and complexity as compared to traditional manufacturing methods while increasing mission-dependent customization of through-depth materials properties. The flight test has three objectives. First, subject the forebody stagnation point of a capsule equipped with additively manufactured TPS (AMTPS) material to peak heat fluxes in excess of 100 $W/cm^2$. Second, capture in-flight data to enable flight reconstruction and AMTPS material thermal response model improvement. Third, recover the capsule with data storage and forebody AMTPS intact to enable post-flight inspection and analysis of AMTPS performance. The flight test trajectory is designed to achieve a peak stagnation point, cold-wall, entry heat flux of 135~$W/cm^2$. Flight mechanics simulations are performed using the Program to Optimize Simulated Trajectories II (POST2) and Monte-Carlo analysis yields statistical percentiles on vehicle performance at key points along the trajectory. Based on the flight mechanics analysis presented in this paper, a prototype capsule was designed, partially fabricated, and underwent preliminary component stress testing in preparation for fabrication of the flight unit capsule. The capsule outer mold line is a modified version of the heritage Mars Microprobe geometry. The capsule has a 0.356~m diameter, a 30~kg mass, and a hypersonic ballistic coefficient of 300~$kg/m^2$. Sensor selection is guided by flight dynamics simulations with the goal of resolving the re-entry heating pulse. On-board instrumentation include forebody and aftbody pressure sensors and thermocouples, a 9-axis IMU, a GPS receiver, and an Iridium satellite modem, all of which collect and store data throughout flight via on-board avionics systems. A two-stage parachute system is designed to decelerate the capsule to touchdown velocities that will not result in significant fracture or deformation of the charred AMTPS material at ground impact.

Flight Mechanics↗

Multiple-Flat-Panel System Displays Multidimensional Data

The NASA Ames hyperwall is a display system designed to facilitate the visualization of sets of multivariate and multidimensional data like those generated in complex engineering and scientific computations. The hyperwall includes a 77 matrix of computer-driven flat-panel video display units, each presenting an image of 1,280 1,024 pixels. The term hyperwall reflects the fact that this system is a more capable successor to prior computer-driven multiple-flat-panel display systems known by names that include the generic term powerwall and the trade names PowerWall and Powerwall. Each of the 49 flat-panel displays is driven by a rack-mounted, dual-central-processing- unit, workstation-class personal computer equipped with a hig-hperformance graphical-display circuit card and with a hard-disk drive having a storage capacity of 100 GB. Each such computer is a slave node in a master/ slave computing/data-communication system (see Figure 1). The computer that acts as the master node is similar to the slave-node computers, except that it runs the master portion of the system software and is equipped with a keyboard and mouse for control by a human operator. The system utilizes commercially available master/slave software along with custom software that enables the human controller to interact simultaneously with any number of selected slave nodes. In a powerwall, a single rendering task is spread across multiple processors and then the multiple outputs are tiled into one seamless super-display. It must be noted that the hyperwall concept subsumes the powerwall concept in that a single scene could be rendered as a mosaic image on the hyperwall. However, the hyperwall offers a wider set of capabilities to serve a different purpose: The hyperwall concept is one of (1) simultaneously displaying multiple different but related images, and (2) providing means for composing and controlling such sets of images. In place of elaborate software or hardware crossbar switches, the hyperwall concept substitutes reliance on the human visual system for integration, synthesis, and discrimination of patterns in complex and high-dimensional data spaces represented by the multiple displayed images. The variety of multidimensional data sets that can be displayed on the hyperwall is practically unlimited. For example, Figure 2 shows a hyperwall display of surface pressures and streamlines from a computational simulation of airflow about an aerospacecraft at various Mach numbers and angles of attack. In this display, Mach numbers increase from left to right and angles of attack increase from bottom to top. That is, all images in the same column represent simulations at the same Mach number, while all images in the same row represent simulations at the same angle of attack. The same viewing transformations and the same mapping from surface pressure to colors were used in generating all the images.

Gundo, Daniel↗

Efficiently predicting pressure-composition-temperature diagrams to discover low-stability metal hydrides

Quantitatively accurate computational predictions of metal hydride thermodynamics are challenging but critical for alloy performance optimization across a multitude of technological domains, including hydrogen storage, compression, purification, and getters. Recent machine learning approaches have demonstrated great success in this area, but can potentially suffer from several shortcomings since they rely on imbalanced experimental training data and can have poor out-of-distribution (ood) test performance. Here, in this study, we circumvent such pitfalls by developing a computationally efficient, first principles-based workflow for direct prediction of metal hydride phase equilibrium, i.e., the pressure-composition-temperature (PCT) diagram. We then demonstrate its utility on predicting low stability hydrides derived from compositionally complex C14 Laves phase AB2 alloys. Specifically, we computationally predict and then experimentally validate an AB 2 alloy series (z < 0.6 for Ti 2−z Zr z CrMnFeNi) with ideal hydriding thermodynamics for a two-stage metal hydride-based compressor for pressurizing boil off from liquefied hydrogen. Importantly, this study lays the groundwork for accurate and efficient discovery/optimization of ood, low-stability hydrides for which purely data-driven approaches lack sufficient accuracy.

08 HYDROGEN↗

Two new SciDAC institutes promote mathematical tools and software technology for high-performance computing

Bigger is often said to be better, and the newest extreme-scale computers certainly are bigger, with millions of processing units. Moreover, the breadth of science performed on the U.S. Department of Energy (DOE) computing facilities is expanding, with new technology such as artificial intelligence emerging. These advances are exciting, creating new opportunities for scientific discovery; however, they also raise new questions for scientists who want to exploit these advances for tackling more complex problems. Will my simulation code be able to utilize the accelerators in extreme-scale computing systems? Can I take advantage of the deepening memory hierarchy in heterogeneous processors? Is there a way around bottlenecks caused by the widening ratio of peak floating-point operations per second to I/0 bandwidth? How can I manage my huge amounts of data effectively? Can I analyze data in situ, or must I transfer it to offline storage for later analysis? To address such questions, DOE announced that it is providing $57.5 million over the next five years for two multidisciplinary teams — FASTMath and RAPIDS2 — to develop new tools and techniques to harness supercomputers for scientific discovery. The teams, called SciDAC Institutes, are part of the Scientific Discovery through Advanced Computing program.

97 MATHEMATICS AND COMPUTING↗

Planning/scheduling techniques for VQ-based image compression

The enormous size of the data holding and the complexity of the information system resulting from the EOS system pose several challenges to computer scientists, one of which is data archival and dissemination. More than ninety percent of the data holdings of NASA is in the form of images which will be accessed by users across the computer networks. Accessing the image data in its full resolution creates data traffic problems. Image browsing using a lossy compression reduces this data traffic, as well as storage by factor of 30-40. Of the several image compression techniques, VQ is most appropriate for this application since the decompression of the VQ compressed images is a table lookup process which makes minimal additional demands on the user's computational resources. Lossy compression of image data needs expert level knowledge in general and is not straightforward to use. This is especially true in the case of VQ. It involves the selection of appropriate codebooks for a given data set and vector dimensions for each compression ratio, etc. A planning and scheduling system is described for using the VQ compression technique in the data access and ingest of raw satellite data.

Short, Nicholas M., Jr.↗

Methods for semi-automated indexing for high precision information retrieval

OBJECTIVE: To evaluate a new system, ISAID (Internet-based Semi-automated Indexing of Documents), and to generate textbook indexes that are more detailed and more useful to readers. DESIGN: Pilot evaluation: simple, nonrandomized trial comparing ISAID with manual indexing methods. Methods evaluation: randomized, cross-over trial comparing three versions of ISAID and usability survey. PARTICIPANTS: Pilot evaluation: two physicians. Methods evaluation: twelve physicians, each of whom used three different versions of the system for a total of 36 indexing sessions. MEASUREMENTS: Total index term tuples generated per document per minute (TPM), with and without adjustment for concordance with other subjects; inter-indexer consistency; ratings of the usability of the ISAID indexing system. RESULTS: Compared with manual methods, ISAID decreased indexing times greatly. Using three versions of ISAID, inter-indexer consistency ranged from 15% to 65% with a mean of 41%, 31%, and 40% for each of three documents. Subjects using the full version of ISAID were faster (average TPM: 5.6) and had higher rates of concordant index generation. There were substantial learning effects, despite our use of a training/run-in phase. Subjects using the full version of ISAID were much faster by the third indexing session (average TPM: 9.1). There was a statistically significant increase in three-subject concordant indexing rate using the full version of ISAID during the second indexing session (p < 0.05). SUMMARY: Users of the ISAID indexing system create complex, precise, and accurate indexing for full-text documents much faster than users of manual methods. Furthermore, the natural language processing methods that ISAID uses to suggest indexes contributes substantially to increased indexing speed and accuracy.

Evaluation Studies↗

Integrated hydrogen recycle system using pressurized multichamber tank

A multi-chambered electrolyte storage tank for a redox flow battery system, may include first and second electrolyte chambers, and a bulkhead, wherein the first and second electrolyte chambers are fluidly coupled to first and second sides of a redox flow battery cell, respectively, the first and second electrolyte chambers include first and second liquid electrolyte volumes, respectively, and the first and second liquid electrolyte volumes are separated by the bulkhead positioned therebetween. In this way, manufacturing and operational complexity of a redox flow battery system can be reduced.

Song, Yang↗