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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Modeling of thermal pressurization in tight claystone using sequential THM coupling: Benchmarking and validation against in-situ heating experiments in COx claystone

We apply thermoporoelasticity and a sequentially coupling technique for modeling thermally-driven coupled Thermo-Hydro-Mechanical (THM) processes in tight claystone. A THM benchmark case with a corresponding analytic solution for thermoporoelasticity under a constant heat loading verifies the model. Thereafter, two in situ heating experiments are simulated for model validation: a smaller-scale heating experiment (TED experiment) and a larger-scale experiment (ALC experiment) in Callovo-Oxfordian (COx) claystone at the Meuse/Haute-Marne underground research laboratory in France. The model exhibits good performance to match the observed temperature and pore pressure evolution for the smaller-scale TED experiment. For the larger-scale ALC experiment, general trends of thermal-pressurization are captured in the modeling, but pressure is underestimated at some monitoring points during cool-down. This indicates that the THM response in the field may be affected by the variability of rock's properties or irreversible or time-dependent mechanical processes that are not included in the current thermoporoelastic model. The main contributions of this work are as follows: (1) we verify and validate the numerical simulator, TOUGH-FLAC, to be a valuable coupled THM modeling tool; (2) prove that the laboratory determined material parameters can be used as reference values for upscaling experiments. However, to better identify and quantify THM processes with modeling of in situ tests, more emphasize should be dedicated to obtaining high-quality mechanical deformation data.

58 GEOSCIENCES↗
DOE OSTI2020

Role of Intact Hydrogen-Bond Networks in Multiproton-Coupled Electron Transfer

The essential role of a well-defined hydrogen-bond network in achieving chemically reversible multiproton translocations triggered by one-electron electrochemical oxidation/reduction is investigated by using pyridylbenzimidazole–phenol models. The two molecular architectures designed for these studies differ with respect to the position of the N atom on the pyridyl ring. In one of the structures, a hydrogen-bond network extends uninterrupted across the molecule from the phenol to the pyridyl group. Experimental and theoretical evidence indicates that an overall chemically reversible two-protoncoupled electron-transfer process (E2PT) takes place upon electrochemical oxidation of the phenol. This E2PT process yields the pyridinium cation and is observed regardless of the cyclic voltammogram scan rate. In contrast, when the hydrogen-bond network is disrupted, as seen in the isomer, at high scan rates (~1000 mV s –1 ) a chemically reversible process is observed with an E 1/2 characteristic of a one-proton-coupled electron-transfer process (E1PT). At slow cyclic voltammetric scan rates (<1000 mV s –1 ) oxidation of the phenol results in an overall chemically irreversible two-proton-coupled electron-transfer process in which the second proton-transfer step yields the pyridinium cation detected by infrared spectroelectrochemistry. In this case, we postulate an initial intramolecular proton-coupled electron-transfer step yielding the E1PT product followed by a slow, likely intermolecular chemical step involving a second proton transfer to give the E2PT product. Insights into the electrochemical behavior of these systems are provided by theoretical calculations of the electrostatic potentials and electric fields at the site of the transferring protons for the forward and reverse processes. Furthermore, this work addresses a fundamental design principle for constructing molecular wires where protons are translocated over varied distances by a Grotthuss-type mechanism.

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

Statistical Complexity of Quantum Learning

Abstract Learning problems involve settings in which an algorithm has to make decisions based on data, and possibly side information such as expert knowledge. This study has two main goals. First, it reviews and generalizes different results on the data and model complexity of quantum learning, where the data and/or the algorithm can be quantum, focusing on information‐theoretic techniques. Second, it introduces the notion of copy complexity, which quantifies the number of copies of a quantum state required to achieve a target accuracy level. Copy complexity arises from the destructive nature of quantum measurements, which irreversibly alter the state to be processed, limiting the information that can be extracted about quantum data. As a result, empirical risk minimization is generally inapplicable. The paper presents novel results on the copy complexity for both training and testing. To make the paper self‐contained and approachable by different research communities, an extensive background material is provided on classical results from statistical learning theory, as well as on the distinguishability of quantum states. Throughout, the differences between quantum and classical learning are highlighted by addressing both supervised and unsupervised learning, and extensive pointers are provided to the literature.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Restoring Escaped Zincate in Rechargeable Alkaline Zinc Batteries with a Seed-in-Nanoshell Design

Rechargeable alkaline zinc batteries are promising candidates for safe and low-cost energy storage, but suffer from ZnO dissolution that causes irreversible active material loss and rapid capacity decay. Here, we report a seed-in-nanoshell ZnO anode architecture that mitigates dissolution by combining physical confinement with electrochemical restoration of dissolved zincate species. ZnO particles are encapsulated within an ion-sieving carbon nanoshell that restricts zincate diffusion, maintains electrical conductivity, and stabilizes repeated solid–solution–solid transformations. Silver (Ag) nanoparticles incorporated into the nanoshell act as zincophilic nucleation seeds, lowering the Zn deposition barrier and directing the redeposition of dissolved zincate back to metallic Zn during charging. This confinement-enabled restoration mechanism converts zincate dissolution from an irreversible loss pathway into a recoverable process, enabling improved performance under harsh test conditions. The anode also delivers 227.9 mAh g −1 at −40 °C. Finally, a scalable tens-of-gram synthesis of ZnO@Ag is demonstrated, underscoring the practical potential of this strategy for advanced aqueous zinc batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

Virtual Time III, Part 1: Unified Virtual Time Synchronization for Parallel Discrete Event Simulation

Algorithms for synchronization of parallel discrete event simulation have historically been divided between conservative methods that require lookahead but not rollback, and optimistic methods that require rollback but not lookahead. In this paper we present a new approach in the form of a framework called Unified Virtual Time (UVT) that unifies the two approaches, combining the advantages of both within a single synchronization theory. Whenever timely lookahead information is available, a logical process (LP) executes conservatively using an irreversible event handler. When lookahead information is not available the LP does not block, as it would in a classical conservative execution, but instead executes optimistically using a reversible event handler. The switch from conservative to optimistic synchronization and back is decided on an event-by-event basis by the simulator, transparently to the model code. UVT treats conservative synchronization algorithms as optional accelerators for an underlying optimistic synchronization algorithm, enabling the speed of conservative execution whenever it is applicable, but otherwise falling back on the generality of optimistic execution. We describe UVT in a novel way, based on fundamental invariants, monotonicity requirements, and synchronization rules. UVT permits zero-delay messages and pays careful attention to tie-handling using superposition. We prove that under fairly general conditions a UVT simulation always makes progress in virtual time. This is Part 1 of a trio of papers describing the UVT framework for PDES, mixing conservative and optimistic synchronization and integrating throttling control.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Ab Initio Studies of Discharge Mechanism of MnO 2 in Deep-Cycled Rechargeable Zn/MnO 2 Batteries

Rechargeable alkaline Zn/MnO 2 batteries are an attractive solution for large-scale energy storage applications. Recently, Bi and Cu additives have been used to increase the cycle life and capacity of rechargeable Zn/MnO 2 batteries, with an equivalent of the full two-electron capacity realized for many cycles, in the absence of zinc. However, the mechanism of the effect of Bi and Cu on the performance of rechargeable Zn/MnO 2 batteries has not been investigated in detail. We apply first-principles density functional computational methods to study the discharge mechanisms of the unmodified and Bi/Cu-modified γ -MnO 2 electrodes in rechargeable alkaline Zn/MnO 2 batteries. Using the results of our calculations, we analyze the possible redox reaction pathways in the γ -MnO 2 electrode and identify the electrochemical processes leading to the formation of irreversible discharge reaction products, such as hausmannite and hetaerolite. Our study demonstrates the possibility of formation of intermediate Bi-Mn and Cu-Mn oxides in deep-cycled Bi/Cu-modified MnO 2 electrodes. The formation of intermediate Bi-Mn and Cu-Mn oxides could reduce the rate of accumulation of irreversible reaction products in the MnO 2 electrode and improve the rechargeability and cyclability of Zn/MnO 2 batteries.

25 ENERGY STORAGE↗
NASA NTRS2005

A Novel Porosity Model for Use in Hydrocode Simulations

Introduction: Numerical modeling of impact cratering has reached a high degree of sophistication; however, the treatment of porous materials still poses a large problem in hydrocode calculations. Porosity plays only a minor role in the formation of large craters on most planetary objects, but impacts on comets are believed to be highly affected by the presence of porosity, which may be as much as 80%. The upcoming Deep Impact Mission (launched January 2005) will provide more detailed data about the composition of a comet (Tempel 1) by shooting a approx.370 kg projectile onto the surface of its nucleus. The numerical simulations of such impact events requires an appropriate model for how pore space in the comet is crushed out during the violent initial stage of the impact event. Most hydro-codes compute the pressure explicitly using an "equation of state" (EOS) for each material, which relates changes in density and internal energy to changes in pressure. The added complication introduced by porosity is that changes in a material s density are due to both the closing of pore space (compaction) and compression of the matrix. The amount of resistance to volume change and the amount of irreversible work done during these two processes is very different; it is far easier to compact a porous material sample than to compress a non-porous sample of the same material. As an alternative to existing porosity models, like the Pdot(alpha) model [1], we present a novel approach for dealing with the compaction of porosity in hydrocode calculations.

Wuennemann, K.↗
NASA NTRS2004

Minimizing Launch Mass for ISRU Processes

The University of Dayton and the Jet Propulsion Laboratory are developing a methodology for estimating the Earth launch mass (ELM) of processes for In-Situ Resource Utilization (ISRU) with a focus on lunar resource recovery. ISRU may be enabling for both an extended presence on the Moon, and for large sample return missions and for a human presence on Mars. To accomplish these exploration goals, the resources recovered by ISRU must offset the ELM for the recovery process. An appropriate figure of merit is the cost of the exploration mission, which is closely related to ELM. For a given production rate and resource concentration, the lowest ELM - and the best ISRU process - is achieved by minimizing capital equipment for both the ISRU process and energy production. ISRU processes incur Carnot limitations and second law losses (irreversibilities) that ultimately determine production rate, material utilization and energy efficiencies. Heat transfer, chemical reaction, and mechanical operations affect the ELM in ways that are best understood by examining the process's detailed energetics. Schemes for chemical and thermal processing that do not incorporate an understanding of second law losses will be incompletely understood. Our team is developing a methodology that will aid design and selection of ISRU processes by identifying the impact of thermodynamic losses on ELM. The methodology includes mechanical, thermal and chemical operations, and, when completed, will provide a procedure and rationale for optimizing their design and minimizing their cost. The technique for optimizing ISRU with respect to ELM draws from work of England and Funk that relates the cost of endothermic processes to their second law efficiencies. Our team joins their approach for recovering resources by chemical processing with analysis of thermal and mechanical operations in space. Commercial firms provide cost inputs for ELM and planetary landing. Additional information is included in the original extended abstract.

England, C.↗
NASA NTRS1990

Energy management analysis of lunar oxygen production

Energy load models in the process of hydrogen reduction of ilmenite for lunar oxygen production are being developed. The load models will be used as a first step to ultimately determine the optimal energy system needed to supply the power requirements for the process. The goal is to determine the energy requirements in the process of hydrogen reduction of ilmenite to produce oxygen. The general approach is shown, and the objectives are to determine the energy loads of the processes in the system. Subsequent energy management studies will be made to minimize the system losses (irreversibilities) and to design optimal energy system power requirements. A number of processes are being proposed as possible candidates for lunar application and some detailed experimental efforts are being conducted within this project at the University of Arizona. Priorities are directed toward developing the energy models for each of the proposed processes being considered. The immediate goals are to identify the variables that would impact energy requirements and energy sources of supply.

Fazzolari, R.↗
DOE OSTI2022

Overcoming Degradation Pathways to Achieve Stable Blue Perovskite Light-Emitting Diodes

Mixed halide (Br/Cl) perovskite nanocrystals (NCs) that represent an advanced blue emitter commonly suffer from spectral instability and poor lifespan; notably, the lack of understanding of the failure mechanisms of these devices has restricted the future progress. Here, we determine that the degradation of CsPbBr x Cl 3– x NCs containing blue light-emitting diodes (LEDs) is due to the combination of two effects. Cl – drift among adjoining NCs under an electric field is found to induce a Cl-deficient material region in multiple NC layers, which dominates the unstable electroluminescence and causes fast degradation in the corresponding devices. In comparison, the monolayer NC devices that feature restricted anion drift pathways exhibit better operational stability; however, excess hole injection is demonstrated to induce irreversible chlorine loss in NCs. Such a process that largely arises from electrochemical oxidation of Cl – initiates a mild device failure in operation of tens of minutes. Through revealing these mechanisms, we modulate the devices’ construction and operational conditions to achieve a longer lifespan.

14 SOLAR ENERGY↗
NASA NTRS1981

Contributions to a thermodynamic model of Earth systems on rivers

A model for the chemical (ground water) erosion and physical (bed load, including sedimentation) erosion of the land was developed. The rudiments of the relation between a regulated sea level (for the past 2500 million years) and the episodic rise and erosion of continents was examined to obtain some notion of the process scalings. Major process scales of about 200 years, 100,000 years, 3 My, 40 My, 300 My were estimated. It was suggested that a program targeted at ecological management would have to become familiar with processes at the first four scales (i.e., from glaciation to the horizontal movement of continents). The study returns to the initial premise. In order to understand and manage Earth biology (life, and modern man), it is necessary minimally to pursue systems' biogeology at a considerable number of process space and time scales via their irreversible thermodynamic couplings.

Iberall, A. S.↗
NASA NTRS1994

Escape, Impacts, and Volatile Budgets

The atmospheres of the terrestrial planets and satellites are generally quite thin, much thinner than might be expected given their relatively high abundances of geochemical volatiles and popular estimates of the available mass of volatile-rich impactors. In some cases a specific deficiency (e.g., water on Venus) implies a specific loss process (a runaway greenhouse effect that promoted irreversible hydrogen escape; same planet). But more generally the absence of atmophiles is broadbased and so argues for broad-based volatile loss. This talk will address the hypothesis that extant planetary atmospheres represent the small residue left between relatively large rates of supply and escape.

Zahnle, K. J.↗
NASA NTRS1997

Origin and Evolution of Planetary Atmospheres

The atmospheres of the terrestrial planets and satellites are generally quite thin, much thinner than might be expected given their relatively high abundances of geochemical volatiles and popular estimates of the available mass of volatile-rich impactors. In some cases a specific deficiency (e.g., water on Venus) implies a specific loss process (a runaway greenhouse effect that promoted irreversible hydrogen escape; same planet). But more generally the absence of atmophiles is broad-based and so argues for broad-based volatile loss. This talk will address the hypothesis that extant planetary atmospheres represent the small residue left between relatively large rates of supply and escape.

Zahnle, K. J.↗
NASA NTRS1977

Early stages in the evolution of the atmosphere and climate on the Earth-group planets

The early evolution of the atmospheres and climate of the Earth, Mars and Venus is discussed, based on a concept of common initial conditions and main processes (besides known differences in chemical composition and outgassing rate). It is concluded that: (1) liquid water appeared on the surface of the earth in the first few hundred million years; the average surface temperature was near the melting point for about the first two eons; CO2 was the main component of the atmosphere in the first 100-500 million years; (2) much more temperate outgassing and low solar heating led to the much later appearance of liquid water on the Martian surface, only one to two billion years ago; the Martian era of rivers, relatively dense atmosphere and warm climate ended as a result of irreversible chemical bonding of CO2 by Urey equilibrium processes; (3) a great lack of water in the primordial material of Venus is proposed; liquid water never was present on the surface of the planet, and there was practically no chemical bonding of CO2; the surface temperature was over 600 K four billion years ago.

Moroz, V. I.↗
DOE OSTI2020

Electron-beam-driven chemical processes during liquid phase transmission electron microscopy

Liquid phase (or liquid cell) transmission electron microscopy (LP-TEM) has been established as a powerful tool for observing dynamic processes in liquids at nanometer to atomic length scales. However, the simple act of observation using electrons irreversibly alters the nature of the sample. A clear understanding of electron beam-driven processes during LP-TEM is required to interpret in situ observations and utilize the electron beam as a stimulus to drive nanoscale dynamic processes. In this review, we discuss recent advances toward understanding, quantifying, mitigating, and harnessing electron beam-driven chemical processes occurring during LP-TEM. We will highlight progress in several research areas, including modeling electron beam-induced radiolysis near interfaces, electron beam-induced nanocrystal formation, and radiation damage of soft materials and biomolecules.

Woehl, Taylor J.↗
DOE OSTI2024

Co(II) Substitution Enhances the Esterase Activity of a de Novo Designed Zn(II) Carbonic Anhydrase

Abstract Carbonic Anhydrases (CAs) have been a target forde novoprotein designers due to the simplicity of the active site and rapid rate of the reaction. The first reported mimic contained a Zn(II) bound to three histidine imidazole nitrogens and an exogenous water molecule, hence closely mimicking the native enzymes’ first coordination sphere. Co(II) has served as an alternative metal to interrogate CAs due to its d 7 electronic configuration for more detailed solution characterization. We present here the Co(II) substituted [Co(II)(H 2 O/OH − )] N (TRIL2WL23H) 3 n+ that behaves similarly to native Co(II) substituted human‐CAs. Like the Zn(II) analogue, the cobalt‐derivative at slightly basic pH is incapable of hydrolyzing p‐nitrophenylacetate (pNPA); however, as the pH is increased a significant activity develops, which at pH values above 10 eventually yields a catalytic efficiency that exceeds that of the [Zn(II)(OH − )] N (TRIL2WL23H) 3 + peptide complex. X‐ray absorption analysis is consistent with an octahedral species at pH 7.5 that converts to a 5‐coordinate species by pH 11. UV‐vis spectroscopy can monitor this transition, giving a pK a for the conversion of 10.3. We assign this conversion to the formation of a 5‐coordinate Co(II)(N imid ) 3 (OH)(H 2 O) species. The pH dependent kinetic analysis indicates the maximal rate (k cat ), and thus the catalytic efficiency (k cat /K m ), follow the same pH profile as the spectroscopic conversion to the pentacoordinate species. This correlation suggests that the chemically irreversible ester hydrolysis corresponds to the rate determining process.

Chemistry↗
DOE OSTI2026

Understanding the Performance Gap between Polycrystalline and Single-Crystal Nickel-Rich Layered Oxide Cathodes

Singe-crystal (SC) nickel-rich layered oxide cathodes, composed of boundary-free particles with high tap density, offer significant advantages in volumetric energy density and mechanical strength compared with polycrystalline (PC) cathode materials. However, as the nickel content increases (≥80%), SC Ni-rich cathodes often suffer from faster performance degradation than PC cathodes of the same composition, and the underlying causes of this discrepancy remain poorly understood. Herein, we reveal the distinct Ni redox behaviors that govern the electrochemical performance of SC and PC Ni-rich cathodes using multiscale and operando characterization techniques. Our results indicate that the increasingly heterogeneous Ni oxidation process in SC cathodes leads to the additional irreversible oxygen redox activity that deteriorates both the mechanical and chemical structures. In contrast, PC cathodes, despite with more pronounced surface reconstruction, exhibit greater chemomechanical stability due to homogeneous redox reactions during charging. Consequently, we find that bulk degradation, more than surface reactions, ultimately leads to fast capacity decay of SC Ni-rich cathodes during cycling. In conclusion, this work offers a comprehensive view on the impact of Ni redox evolutions on the chemomechanical stability in Ni-rich layered oxide cathodes, providing new insights into the longstanding performance gap between SC and PC cathodes, and guiding the rational design of Ni-rich cathode architectures.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Probing three-dimensional mesoscopic interfacial structures in a single view using multibeam X-ray coherent surface scattering and holography imaging

Abstract Visualizing surface-supported and buried planar mesoscale structures, such as nanoelectronics, ultrathin-film quantum dots, photovoltaics, and heterogeneous catalysts, often requires high-resolution X-ray imaging and scattering. Here, we discovered that multibeam scattering in grazing-incident reflection geometry is sensitive to three-dimensional (3D) structures in a single view, which is difficult in conventional scattering or imaging approaches. We developed a 3D finite-element-based multibeam-scattering analysis to decode the heterogeneous electric-field distribution and to faithfully reproduce the complex scattering and surface features. This approach further leads to the demonstration of hard-X-ray Lloyd’s mirror interference of scattering waves, resembling dark-field, high-contrast surface holography under the grazing-angle scattering conditions. A first-principles calculation of the single-view holographic images resolves the surface patterns’ 3D morphology with nanometer resolutions, which is critical for ultrafine nanocircuit metrology. The holographic method and simulations pave the way for single-shot structural characterization for visualizing irreversible and morphology-transforming physical and chemical processes in situ or operando .

47 OTHER INSTRUMENTATION↗