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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Interface‐Controlled Redox Chemistry in Aqueous Mn 2 ⁺/MnO₂ Batteries

Manganese dioxide (MnO 2 ) deposition/dissolution (Mn 2+ /MnO 2 ) chemistry, involving a two-electron-transfer process, holds promise for safe and eco-friendly large-scale energy storage. However, challenges like electrode/electrolyte interface environment fluctuations (H + and H 2 O activity), irreversible Mn degradation, and limited understanding of degradation mechanisms hinder the reversibility of the Mn 2+ /MnO 2 conversion. This study demonstrates a vanadyl/pervanadyl (VO 2+ /VO 2 + ) redox-mediated interface designed for high-energy Mn 2+ /MnO 2 batteries. Unlike flow systems, this work uncovers, for the first time, the mechanism of a static redox-mediated interface in regulating interfacial H + and H 2 O activities. Significantly, the VO 2+ /VO 2 + chemical redox mediation targets Mn 3+ intermediates, suppressing their hydrolysis and enabling 100% Mn 2+ /MnO 2 conversion. The redox-mediated interface enhances the Mn redox electron transfer process, achieving a stable ≈95% coulombic efficiency and ultrahigh capacity of 100 mAh cm −2 with an areal energy density of 111 mWh cm −2 , outperforming flow systems. The electrode also exhibits an average specific capacity of 593 mAh g −1 , approaching the theoretical limit of 616 mAh g −1 , and a specific energy density of 721 Wh kg −1 at high MnO 2 loadings (50–150 mg cm −2 ). Furthermore, the findings highlight the critical role of interfacial redox mediation in regulating H + and H 2 O activities and underscore the significance of interface dynamics.

Xue, Xinzhe [University of California, Santa Cruz,↗
DOE OSTI2022

Bayesian Active Learning for Scanning Probe Microscopy: From Gaussian Processes to Hypothesis Learning

Recent progress in machine learning methods and the emerging availability of programmable interfaces for scanning probe microscopes (SPMs) have propelled automated and autonomous microscopies to the forefront of attention of the scientific community. However, enabling automated microscopy requires the development of task-specific machine learning methods, understanding the interplay between physics discovery and machine learning, and fully defined discovery workflows. This, in turn, requires balancing the physical intuition and prior knowledge of the domain scientist with rewards that define experimental goals and machine learning algorithms that can translate these to specific experimental protocols. Here, we discuss the basic principles of Bayesian active learning and illustrate its applications for SPM. We progress from the Gaussian process as a simple data-driven method and Bayesian inference for physical models as an extension of physics-based functional fits to more complex deep kernel learning methods, structured Gaussian processes, and hypothesis learning. These frameworks allow for the use of prior data, the discovery of specific functionalities as encoded in spectral data, and exploration of physical laws manifesting during the experiment. Here, the discussed framework can be universally applied to all techniques combining imaging and spectroscopy, SPM methods, nanoindentation, electron microscopy and spectroscopy, and chemical imaging methods and can be particularly impactful for destructive or irreversible measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

In situ evidence of rapid, vertical, irreversible transport of lower tropospheric air into the lower tropical stratosphere by convective cloud turrets and by larger-scale upwelling in tropical cyclones

The STEP tropical objectives were successfully met during the flight experiments conducted from Darwin, Australia, January 16 to February 16, 1987. Necessary and sufficient measurements were made in, above, and downwind from very cold cirrus clouds, produced by three convective cloud types, to demonstrate irreversible mass transports into and dehydration in the lower tropical stratosphere. The three types are defined and described in terms of the physical processes that produce them and illustrated by examples derived from in situ and remote measurements. Intense solar heating is shown to produce, in addition to the usual vertical, sea breeze circulations normal to the coastline, an unusual pair of continental spanning, horizontal circulations. An upper tropospheric-lower stratospheric anticyclonic circulation, inclined upward toward the tropics, contributes to the dehydration of dissipating cirrus anvils and intensifies the upper level, tropical easterlies. The lower tropospheric cyclonic circulation with tropical westerlies and extratropical easterlies is in direct conflict with the normal tropical easterlies and extratropical westerlies. Impulsive switches between these two opposing lower-level wind systems create conditions favorable for each of these cloud types and explain the summer season's aperiodic variability.

Danielsen, Edwin F.↗
NASA NTRS2013

Stratosphere-to-Troposphere Transport Revealed by Ground-based Lidar and Ozonesonde at a Midlatitude Site

This paper presents ozone structures measured by a ground-based ozone lidar and ozonesonde at Huntsville, Alabama, on 27-29 April 2010 originating from a stratosphere-to-troposphere transport event associated with a cutoff cyclone and tropopause fold. In this case, the tropopause reached 6 km and the stratospheric intrusion resulted in a 2-km thick elevated ozone layer with values between 70 and 85 ppbv descending from the 306-K to 298-K isentropic surface at a rate of 5 km day1. The potential temperature was provided by a collocated microwave profiling radiometer. We examine the corresponding meteorological fields and potential vorticity (PV) structures derived from the analysis data from the North American Mesoscale model. The 2-PVU (PV unit) surface, defined as the dynamic tropopause, is able to capture the variations of the ozone tropopause estimated from the ozonesonde and lidar measurements. The estimated ozone/PV ratio, from the measured ozone and model derived PV, for the mixing layer between the troposphere and stratosphere is approximately 41 ppbv/PVU with an uncertainty of approximately 33%. Within two days, the estimated mass of ozone irreversibly transported from the stratospheric into the troposphere is between 0.07 Tg (0.9 10(exp33) molecules) and 0.11 Tg (1.3 10(exp33) molecules) with an estimated uncertainty of 59%. Tropospheric ozone exhibited enormous variability due to the complicated mixing processes. Low ozone and large variability were observed in the mid-troposphere after the stratospheric intrusion due to the westerly advection including the transition from a cyclonic system to an anticyclonic system. This study using high temporal and vertical-resolution measurements suggests that, in this case, stratospheric air quickly lost its stratospheric characteristics once it is irreversibly mixed down into the troposphere.

Kuang, Shi↗
DOE OSTI2020

Coefficient of Thermal Expansion during Ratchet Growth of TATB Compactions

Triamino trinitrobenzene (TATB) is an insensitive high explosive, meaning that it is quite immune from accidental detonation and only performs in appropriately engineered configurations. While this is advantageous for applications, the TATB crystal is graphitic and possesses significant thermal and mechanical anisotropy. Compactions of TATB crystals, with or without binder, have been shown to have oriented TATB crystals that relate to the pressing geometry and process, and this TATB texture necessarily imparts microscale and macroscale anisotropy to the compaction. By a mechanism not fully understood, thermal cycling results in irreversible volume expansion (also called ratchet growth) of the compaction likely by creating stress points on the microscale. Changes in density caused by thermal cycling can certainly effect the explosive performance. Our past characterization of the ratchet growth phenomenon has focused on the magnitude of the irreversible strain as measured before and after a thermal cycle. Finally, in the work presented here, we analyze the evolving thermal expansion behavior during the ascending and descending temperature ramps, providing further insight into the material changes taking place during the ratchet growth phenomenon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2021

Multiscale Catalytic Fast Pyrolysis of Grindelia Reveals Opportunities for Generating Low Oxygen Content Bio-Oils from Drought Tolerant Biomass

Grindelia squarrosa (curlycup gumweed) biomass possesses unique biochemistry, cell wall composition, and leaf architecture tailored for prolific growth in arid and semiarid climates. Most notably, this plant has developed high levels of extractable resins that have high effective H/C eff ratios ((mol H - 2 x mol O)/mol C), which is hypothesized to lead to low coke formation during catalytic fast pyrolysis (CFP) over the ZSM-5 catalyst. In microscale experiments with high ZSM-5 loadings (biomass-to-catalyst mass ratio (B/C) ~ 0.1), in situ CFP generated high yields of aromatic hydrocarbons (30% carbon yield) while ex situ CFP favored aliphatic hydrocarbons (25% carbon yield). The difference between the two configurations was attributed to the constant catalyst temperature during ex situ CFP. Deactivation leading to partially deoxygenated vapor products occurred rapidly until B/C ≤ 0.5 by the adsorption of organic species blocking access to acid sites inside the micropores of the catalyst. This was followed by more gradual deactivation leading to primary vapor breakthrough, which we attribute to coke formation on acid sites on the external surface of ZSM-5 crystallites. Noncatalytic fast pyrolysis of Grindelia in a bench scale reactor produced oils with oxygen content (18 wt % on dry basis) and carbon yield (33%) comparable to those of CFP of woody biomass. The CFP of Grindelia further reduced the oxygen content to 7 wt % for in situ CFP and 4 wt % for ex situ CFP at B/C of 2-3. The good deoxygenation was attributed to a combination of a high H/C eff ratio and overall better quality of the pyrolysis vapors that were passed over the ZSM-5 catalyst. The high inorganic content of the Grindelia likely catalyzed pyrolysis to remove oxygenated coke precursors. This integrated CFP study demonstrated that Grindelia could be an important feedstock for generating stabilized noncatalytic and CFP oils for downstream processing into fuels and/or extraction of high-value chemicals. The preprocessing of this feedstock will be required to remove inorganics, which cause an irreversible deactivation of ZSM-5.

BIOMASS FUELS↗
DOE OSTI2023

Targeting Aspergillus allergen oryzin with a chemical probe at atomic precision

We report the molecular basis of Aspergillus fumigatus oryzin, allergen Asp f 13, or alkaline proteinase ALP1, containing the sequence motif His–Asp–Ser of the subtilisin family, structure, and function at atomic detail. Given the resolution of the data (1.06 Å), we use fragment molecular replacement with ideal polyalanine α-helices to determine the first crystal structure of oryzin. We probe the catalytic serine through formation of an irreversible bond to a small molecule compound, specifically labeling it, describing the amino acid residues performing the catalytic function. Defined by a self-processed pro-peptide, the active site architecture shapes up pocket-like subsites that bind to and unveil the S1′–S4′ substrate binding preferences. We use molecular modeling to dock a model of the pro-peptide in the S1–S4 region and to dock collagen along the active site cleft. Opposite to the face harboring the catalytic serine, the enzyme binds to a calcium ion in a binding site created by backbone flipping. We use thermal unfolding to show that this metal ion provides structural stability. With no known host inhibitor identified thus far, this structure may hasten the progress of developing new therapeutic agents for diseases caused by pathogenic fungi.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1999

Geochemical Evidence for a Terrestrial Magma Ocean

The aftermath of phase separation and crystal-liquid fractionation in a magma ocean should leave a planet geochemically differentiated. Subsequent convective and other mixing processes may operate over time to obscure geochemical evidence of magma ocean differentiation. On the other hand, core formation is probably the most permanent, irreversible part of planetary differentiation. Hence the geochemical traces of core separation should be the most distinct remnants left behind in the mantle and crust, In the case of the Earth, core formation apparently coincided with a magma ocean that extended to a depth of approximately 1000 km. Evidence for this is found in high pressure element partitioning behavior of Ni and Co between liquid silicate and liquid iron alloy, and with the Ni-Co ratio and the abundance of Ni and Co in the Earth's upper mantle. A terrestrial magma ocean with a depth of 1000 km will solidify from the bottom up and first crystallize in the perovskite stability field. The largest effect of perovskite fractionation on major element distribution is to decrease the Si-Mg ratio in the silicate liquid and increase the Si-Mg ratio in the crystalline cumulate. Therefore, if a magma ocean with perovskite fractionation existed, then one could expect to observe an upper mantle with a lower than chondritic Si-Mg ratio. This is indeed observed in modern upper mantle peridotites. Although more experimental work is needed to fully understand the high-pressure behavior of trace element partitioning, it is likely that Hf is more compatible than Lu in perovskite-silicate liquid pairs. Thus, perovskite fractionation produces a molten mantle with a higher than chondritic Lu-Hf ratio. Arndt and Blichert-Toft measured Hf isotope compositions of Barberton komatiites that seem to require a source region with a long-lived, high Lu-Hf ratio. It is plausible that that these Barberton komatiites were generated within the majorite stability field by remelting a perovskite-depleted part of the upper mantle transition zone.

Agee, Carl B.↗
DOE OSTI2024

Cellulose Nanofibrils Dewatered with Poly(Lactic Acid) for Improved Bio-Polymer Nanocomposite Processing

Cellulose nanofibrils (CNFs) have theoretically ideal properties for bio-based composite applications; however, the incorporation of these materials into polymers is made challenging by the strong binding of water to CNFs and the irreversible agglomeration of CNFs during drying. Previous methods used “contact dewatering”, wherein the addition of wood flour (WF) to CNFs facilitated the mechanical removal of water from the system via cold pressing, which showed potential in producing dried CNF fibrils attached to wood fibers for biocomposite applications. In this work, the viability of contact dewatering with poly(lactic) acid (PLA) powder for PLA/CNF composites was evaluated. The energy efficiency of dewatering, preservation of nanoscale CNF morphology, and mechanical properties were examined by mixing wet CNFs with pulverized PLA at various loading levels, pressing water out of the system, and compression molding and shear mixing composites for testing. The most impressive results from this dewatering method were the preservation of micron-to-nanoscale fibers with high aspect ratios in PLA-CNF composites; increased strength and modulus of 1.7% and 4.2%, respectively, compared to neat PLA; equivalent or better properties than spray-dried nanocellulose at similar loading levels; and an 11-194x reduction in drying energy compared to spray-drying CNFs.

Chemistry↗
DOE OSTI2022

Coefficient of Thermal Expansion Evolution during Ratchet Growth of PBX 9502 and Neat TATB

The Plastic-Bonded Explosive (PBX) 9502 is comprised of the insensitive high explosive TATB (triamino trinitrobenzine) crystals coated in FK-800 polymer binder and isostatically pressed. The TATB crystals have a graphitic, plate-like morphology and possess significant thermal and mechanical anisotropy. Compactions of neat TATB or TATB-based composites (like PBX 9502) have been shown to have TATB crystals that are oriented during the pressing process giving rise to TATB texture and resulting in micro- and macro-scale anisotropy of the compaction. Thermal cycling of the compactions results in irreversible volume expansion (or ratchet growth) likely by creating stress points on the microscale. However, the actual mechanism behind this expansion is not fully understood. Previous characterization of the ratchet growth phenomenon has focused on the magnitude of the irreversible strain as measured before and after a thermal cycle. In the work presented here, we analyze the evolving thermal expansion behavior during the ascending and descending temperature ramps and compare differences observed due to the presence/absence of binder in the compaction.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
DOE OSTI2020

Anthracene Diphosphate Ligands for CdSe Quantum Dots; Molecular Design for Efficient Upconversion

Quantum dot (QD)-sensitized photon upconversion follows a multi-step energy transfer process from the QD to transmitter ligand to a soluble annihilator. Using a novel 10-R-anthracene-1,8-diphosphoric acid (R = octyl, 2- hexyldecyl, phenyl) ligand with high binding affinity for CdSe QD surfaces, we demonstrate a photon upconversion process that is limited by the transmitter to annihilator transfer efficiency. Using 1 H NMR spectroscopy, we demonstrate that these bidentate diphosphate ligands rapidly and irreversibly displace two carboxylate ligands. These ligands mediate energy transfer from the photoexcited QDs to a triplet annihilator (1,10-diphenylanthracene), producing overall photon upconversion quantum efficiencies as high as 17%, the highest for QDs with no shells. In conclusion, transient absorption spectroscopy shows that the anthracene dihydrogen phosphate (ADP) ligand supports a 3.4 fold longer triplet state lifetime compared to 9-anthracene carboxylic acid (299.9 ± 9.5 vs 88.2 ± 2.1 μs), increasing the probability of energy transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Statistics and thermodynamics of fracture

A probabilistic model of the fracture processes unifying the phenomenological study of long term strength of materials, fracture mechanics and statistical approaches to fracture is briefly outlined. The general framework of irreversible thermodynamics is employed to model the deterministic side of the failure phenomenon. The stochastic calculus is used to account for thg failure mechanisms controlled by chance; particularly, the random roughness of fracture surfaces.

Chudnovsky, A.↗
NASA NTRS2012

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.

Hagh, Nader↗
DOE OSTI2025

Modeling aerosol bolus inhalations in the human lung with the multiple path particle deposition model: Comparison with experimental data

Existing one-dimensional (1D) models of aerosol dosimetry often ignore mixing mechanisms of inhaled aerosols during their transport in the lung. This mixing or aerosol dispersion results from different physical mechanisms in different regions of the lung. It is a higher order effect, which cannot be directly captured in 1D modeling approaches, and thus is sometimes modeled as a diffusive process. Here, in this study, we improved our recently developed alveolar mixing module incorporated in the multiple path particle dosimetry model (MPPD) to account for flow irreversibility and particle trapping in the alveolar spaces, as well as mixing occurring in the tracheobronchial region. This new version of MPPD was coupled with CFPD-based predictions of aerosol bolus dispersion in the oral airway. The model was used to predict the deposition, dispersion, and mode shift of aerosol bolus inhaled at different penetration depths within the lung for breathing patterns and particle size matching those used in a previous experimental study (Darquenne et al., 2016). Even though a quite simplified approach was used, the computations appear to describe subject-specific and test-specific experimental data reasonably well. The proposed combined dispersion-deposition model can be a useful tool for targeted drug delivery and also for exposure health risk assessment.

MPPD↗
NASA NTRS1989

Characterization of long-term extension of isolated cell walls from growing cucumber hypocotyls

Walls from frozen-thawed cucumber (Cucumis sativus L.) hypocotyls extend for many hours when placed in tension under acidic conditions. This study examined whether such "creep" is a purely physical process dependent on wall viscoelasticity alone or whether enzymatic activities are needed to maintain wall extension. Chemical denaturants inhibited wall creep, some acting reversibly and others irreversibly. Brief (15 s) boiling in water irreversibly inhibited creep, as did pre-incubation with proteases. Creep exhibited a high Q10 (3.8) between 20 degrees and 30 degrees C, with slow inactivation at higher temperatures, whereas the viscous flow of pectin solutions exhibited a much lower Q10 (1.35). On the basis of its temperature sensitivity, involvement of pectic gel-sol transitions was judged to be of little importance in creep. Pre-incubation of walls in neutral pH irreversibly inactivated their ability to creep, with a half-time of about 40 min. At 1 mM, Cu2+, Hg2+ and Al3+ were strongly inhibitory whereas most other cations, including Ca2+, had little effect. Sulfhydryl-reducing agents strongly stimulated creep, apparently by stabilizing wall enzyme(s). The physical effects of these treatments on polymer interactions were examined by Instron and stress-relaxation analyses. Some treatments, such as pH and Cu2+, had significant effects on wall viscoelasticity, but others had little or no apparent effect, thus implicating an enzymatic creep mechanism. The results indicate that creep depends on relatively rugged enzymes that are firmly attached to or entangled in the wall. The sensitivity of creep to SH-reducing agents indicates that thiol reduction of wall enzymes might provide a control mechanism for endogenous cell growth.

NASA Program Space Biology↗
NASA NTRS2004

Organic Modification of a Layered Silicate by Co-Ion Exchange of an Alkyl Ammonium and a Mono-Protonated Diamine

Co-Ion exchange of the interlayer cations of a layered silicate with a mono-protonated aromatic diamine and an alkyl ammonium ion into the silicate galleries. The presence of the alkyl ammonium ion provides low oligomer melt viscosity during processing. The presence of the diamine allows chemical reaction between the silicate surface modification and the monomers. This reaction strengthens the polymer silicate interface, and ensures irreversible separation of the individual silicate layers. Improved polymer thermal oxidative stability and mechanical properties are obtained.

Sandi G Campbell↗
DOE OSTI2020

Electrolyte-phobic Surface for the Next-Generation Nanostructured Battery Electrodes

Nanostructured electrodes are among the most important candidates rationally designed to enable high capacity battery chemistry. Nanostructures can solve issues such as the volume change and mechanical fragmentations. However, the high surface area they usually possess would decrease the Coulombic efficiencies, since the side chemical reactions scale with surface area. Moreover, electrodes comprised of nanomaterials have significant intakes of liquid electrolytes, which reduces the overall energy density and increases the cost of the battery. Here we present a new strategy of limiting effective surface area by introducing an “electrolyte-phobic surface”. In this study, a porous Si anode functions as a model material to demonstrate this concept. Silicon boasts high theoretical capacity, but experiences large volume change during its lithiation and delithiation processes. Porous Si can address this volume change problem with the buffer effect of its inner pores. However, porous silicon shows low initial Coulombic efficiencies and high irreversible lithium loss, owing to its intrinsic high surface area. In this report, a covalently linked perfluorinated surface coating layer on porous Si particles serves as an electrolyte-phobic protection layer, minimizing the accessible surface area for the electrolytes, decreasing the side reactions between the electrolyte and Si surface, and thus significantly enhancing the initial Coulombic efficiencies, up to ~88% compared to ~60% for the pristine porous silicon. Meanwhile, the electrolyte-phobic protection layer of Si particles keeps the silicon surface compatible with the conventional polyvinylidene fluoride (PVDF) binder, which helps to stabilize the Si electrode for long-term battery cycling.

Qian, Chenxi↗
NASA NTRS1979

Release adiabat measurements on minerals: The effect of viscosity

The current inversion of pressure-particle velocity data for release from a high pressure shock state to a pressure-density path is analyzed. It is assumed that the release process is isentropic. It was shown that for geological materials below stresses of 150 GPa, the effective viscosity must be 1000 kg/m/s in order that the viscous (irreversible) work carried out on the material in the shock state remains small compared to the mechanical work recovered upon adiabatic rarefaction. The available data pertaining to the offset of the Rayleigh line from the Hugoniot for minerals, the magnitude of the shear stress in the high pressure shock state for minerals, and the direct measurements of the viscosities of several engineering materials shocked to pressures below 150 GPa yield effective viscosities of 1000 kg/m/s or less. An inferance that this indicates that the conditions for isentropic release of minerals from shock states are achieved, and a conclusion that the application of the Riemann integral to obtain pressure-density states along the release adiabats of minerals in shock experiments is valid are made.

Jeanloz, R.↗