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DOE OSTI2025

Non-destructive electrochemical diagnosis of failure mechanisms in aqueous zinc batteries

The early detection of secondary reactions that affect the life and performance of zinc manganese oxide batteries requires a shift from conventional time-consuming and often destructive procedures to rapid lifetime-predictive techniques. In this work, an electrochemical approach is employed to elucidate independent signatures for four common types of failure mechanisms in zinc manganese dioxide (Zn||MnO2) batteries—namely, the loss of zinc inventory, the loss of active material at the cathode, electrolyte depletion, and increased cell impedance. Our findings, specific to coin cell configurations, reveal that each induced failure mechanism can be distinctively modeled and identified based on responses from the rest voltage and columbic-efficiency data for prompt detection. For instance, electrolyte depletion response manifests a distinctive abrupt (>80 %) decrease in columbic efficiency (CE) and charge-rest voltage (Vc) while the discharge-rest voltage remained constant at ~1.3 V. Furthermore, electrolyte rejuvenation of the cell increased the CE to >95 % and restored Vc from ~0.3 to >1.7 V. Recovery experiments and reference performance tests demonstrated consistency between electrochemical descriptors and their associated failure mechanisms. Further, the outcomes of this work provide valuable insights and data models for some of the dominant failure mechanisms present in zinc manganese battery chemistries, which are beneficial to accelerated early-lifetime diagnosis and advancement of Zn batteries development.

25 ENERGY STORAGE↗

DOE OSTI2023

Spectroscopic Investigations of Molecular Symmetry Breakdown

This project addressed precise measurements of the spectra of molecules to address fundamental questions in chemical physics in the realm of nuclear spin symmetries and their breakdown in molecules, and parity non-conservation caused by the weak nuclear force. Nuclear spin symmetry is intimately connected to parity in symmetrical molecules and plays a central role in the physical and chemical properties of symmetric molecules, their collisional relaxation, and the establishment of thermodynamic equilibrium in an ensemble. Such effects are present in every molecular system or process, but their small size means they are often only directly observable under special conditions. However, their measurement is of fundamental, and often practical importance, and strongly relates to the themes of coherence in light and matter in the recent Basic Energy Sciences Advisory Committee (BESAC) report “Challenges at the Frontiers of Matter and Energy: Transformative Opportunities for Discovery Science”. We begin by addressing lifetime broadening of spectroscopic lines caused by self-collisions in acetylene, where efficient resonant rotational energy transfer between a pair of molecules separated in energy by rotational quantum number ΔJ = ± 2, can result in a different pressure broadening for ortho- and para- nuclear spin state molecules. This work was prompted by a controversial report [Iwakuni et al. Phys. Rev Letts. 117 (2016) 143902] of the observation of such an effect in the v 1 +v 3 combination band transition of acetylene discussed in the original proposal. After delays caused by the COVID-19 pandemic, we have completed these measurements and a paper was published in the Journal of Chemical Physics describing the work. The measurements pointed out that the use of an approximate model in the analysis of the original work was the cause of the erroneous conclusion that ortho and para acetylene molecules had substantially different collisional lifetime broadening. In the process, much improved broadening measurements have been made that will permit more reliable modeling of the effects in the future. Subsequently, we have completed a new set of measurements of self- and nitrogen-collisional broadening at a series of low and intermediate temperatures to characterize the temperature dependence of the effects in the molecule. This work is currently being analyzed and will be the subject of a paper to be published in the relatively near future. In addition, some very preliminary measurements of CH 4 as described in the proposal, have been completed. If facilities and time permit, these will continue as an undergraduate research project.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS1999

Candle Flames in Microgravity

This work is a study of a candle flame in a microgravity environment. The purpose of the work is to determine if a steady (or quasi-steady) flame can exist in a microgravity environment, study the characteristics of the steady flame, investigate the pre-extinction flame oscillations observed in a previous experiment in more detail, and finally, determine the nature of the interactions between two closely spaced candle flames. The candle flame in microgravity is used as a model of a non-propagating, steady-state, pure diffusion flame. The present work is a continuation of two small-scale, space-based experiments on candle flames, one on the Shuttle and the other on the Mir OS. The previous studies showed nearly steady dim blue flames with flame lifetimes as high as 45 minutes, and 1 Hz spontaneous flame oscillations prior to extinction. The present paper summarizes the results of the modeling efforts to date.

Daniel L Dietrich↗

DOE OSTI2022

Manifestation of postcollision interaction in Krypton LMN Auger spectra following K-shell photoionization

In this work, we report on an experimental and theoretical study of post-collision interaction (PCI) effects on L 2 -M 4,5 N 2,3 Auger electrons measured above the Kr K-edge in which L 2 vacancies are primarily generated by KL 2 x-ray emission. Such cascade processes, in which a deep inner-shell vacancy decays first by x-ray emission followed by Auger electron emission, is a strong decay mode in heavy atoms. The L 2 -M 4,5 N 2,3 Auger electron peak is observed to become increasingly asymmetric with a shifting peak maximum as the absorbed x-ray energy approaches the K-shell ionization threshold. This is attributed to PCI energy exchanges of the Auger electron with the 1s photoelectron. To model the PCI effects, we have applied a semiclassical approach modified to account for the combined lifetimes of the K and L 2 hole states. In addition, our analysis treats several closely spaced Auger transitions with final ionic states having different terms and angular momenta.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2025

Reaching the prolate-oblate boundary at 𝑁=116 via first fragmentation of a 198 Pt beam: Sharp transition to triaxiality in 189 Ta

High-spin isomers in very-neutron-rich 𝐴≈190 Hf-Ta-W nuclei were populated via the pioneering fragmentation of a 198 Pt primary beam at the National Superconducting Cyclotron Laboratory. The nuclei were implanted in a Si detector stack surrounded by the Gamma-Ray Energy Tracking In-beam Nuclear Array (GRETINA) to detect delayed 𝛾 rays, providing first level schemes using 𝛾−𝛾 coincidence data from isomeric decays in this previously inaccessible region of the nuclear chart. Here, a sudden transition to a strong triaxial shape is observed in the very-neutron-rich 189 Ta (𝑁 = 116) nucleus from axially prolate shapes in lighter Ta isotopes, providing a critical experimental benchmark for competing theoretical predictions of nuclear-shape evolution.

150 ≤ A ≤ 189↗

DOE OSTI2021

The Development of Catalysts for Upgrading of Pyrolysis Vapor for Refinery Feedstocks and Intermediates: Cooperative Research and Development, CRADA Number CRD-12-00497 (Final Report)

Fast pyrolysis of biomass with vapor phase upgrading (VPU) can produce refinery feedstocks or intermediates that can meet the Department of Energy’s goal of cost-competitive hydrocarbon fuels by 2017. A key technical barrier for this technology is the lack of selective, cost effective catalysts that can produce high yields of fuel-appropriate hydrocarbons from the pyrolysis vapors. In overcoming this barrier, it will be important to engage leading catalyst development companies to devote their resources and expertise to the development of these materials. Thus, we propose a Cooperative Research and Development Agreement (CRADA) between the National Renewable Energy Laboratory (NREL), a world leader in biomass pyrolysis research and Johnson Matthey (JM), a world leader in the production of advanced catalyst materials to develop and test novel catalysts for efficient VPU. Through its Intercat Inc. subsidiary in Savannah, Ga., Johnson Matthey is internationally recognized as a leader in zeolite-based vapor phase upgrading in refinery duties and an emerging developer of biomass conversion technologies. The research and development efforts described in the proposed work will build upon existing collaborations between NREL and JM and play to the strengths of both institutions. NREL will analyze the composition of pyrolysis vapors as an input to catalyst design, screen and test catalysts, characterize the resulting oil and conduct techno-economic analysis. Catalyst samples will be produced and funded by JM. JM will design and synthesize catalysts, characterize fresh and used catalysts and develop catalyst supports needed to achieve commercially meaningful lifetimes. The project will span catalyst development and testing from the fundamental stage using quantum mechanical modeling and chemical reaction analysis to catalyst screening to integrated pilot studies.

09 BIOMASS FUELS↗

DOE OSTI2024

Microstructural Engineering and Accelerated Test Method Development to Achieve Low Cost, High Performance Solutions for Hydrogen Storage and Delivery

This project made advancements in developing lower cost steel alloys with novel microstructural design for use in hydrogen refueling infrastructure such as storage, compressors, and dispensing components, and utilizing accelerated test methods to efficiently evaluate variations in alloy and microstructure design. The project specifically sought to design alloys with lower nickel contents to reduce alloy cost, which was accomplished through substituting manganese for nickel along with other alloy additions to control deformation characteristics known to be important for hydrogen embrittlement resistance. Through Mn substitutions for nickel, austenitic and duplex austenite-ferrite steels were successfully developed with lower cost than currently available commercial stainless steel products that are employed for hydrogen refueling infrastructure. The steels were processed to achieve comparable strength and toughness in hydrogen environments as the commercially available steels containing high Ni contents. To evaluate mechanical performance in hydrogen, a testing methodology was employed to compare ubiquitous laboratory testing using electrochemical hydrogen charging in a liquid electrolyte to less accessible high pressure gaseous testing. While the application of these steels is in high pressure gaseous environments, the electrochemical hydrogen charging tests produced comparable results. Additionally, the Los Alamos Neutron Scatting Center enabled characterization of deformation mechanisms of the steel alloys in the presence of hydrogen, which has been associated with steel alloy characteristics associated with hydrogen embrittlement. Finally, a fracture mechanics based test bed model was developed to predict the influence of hydrogen gas pressure and fatigue conditions on fatigue lifetimes of pressure vessel steels. Together, these developments can be employed to enable lower cost hydrogen fueling infrastructure and more reliable prediction of steel alloy components in hydrogen service conditions. In particular, the newly alloys have the potential to replace stainless steels, having demonstrated comparable performance at substantially reduced cost.

08 HYDROGEN↗

DOE OSTI2024

Evaluation of the Mechanical Properties of Cast and Wrought CF8C-Plus Relevant to ASME Code Case Qualification

The mechanical behavior of a cast form of an advanced austenitic stainless steel, CF8C-Plus, is compared with that of its wrought equivalent in terms of both tensile and creep-rupture properties and estimated allowable stress values for pressurized service at temperatures up to about 850°C. A traditional Larson-Miller parametric model is used to analyze the creep-rupture data and to predict long-term lifetimes for comparison of the two alloy types. The cast CF8C-Plus exhibited lower yield and tensile strengths, but higher creep strength compared to its wrought counterpart. Two welding methods, shielded-metal-arc welding (SMAW) and gas-metal-arc welding, met the weld qualification acceptance criteria in ASME BPVC Section IX for the cast CF8C-Plus. However, for the wrought CF8C-Plus, while SMAW and gas-tungsten-arc welding passed the tensile acceptance criteria, they failed the side bend tests due to lack of fusion or weld metal discontinuities.

Chen, Xiang↗

NASA NTRS1985

Viscoplastic constitutive relationships with dependence on thermomechanical history

Experimental evidence of thermomechanical history dependence in the cyclic hardening behavior of some common high-temperature structural alloys is presented with special emphasis on dynamic metallurgical changes. The inadequacy of formulating nonisothermal constitutive equations solely on the basis of isothermal testing is discussed. A representation of thermoviscoplasticity is proposed that qualitatively accounts for the observed hereditary behavior. This is achieved by formulating the scalar evolutionary equation in an established viscoplasticity theory to reflect thermomechanical path dependence. To assess the importance of accounting for thermomechanical history dependence in practical structural analyses, two qualitative models are specified: (1) formulated as if based entirely on isothermal information; (2) to reflect thermomechanical path dependence using the proposed thermoviscoplastic representation. Predictions of the two models are compared and the impact the calculated differences in deformation behavior may have on subsequent lifetime predictions is discussed.

Robinson, D. N.↗

NASA NTRS1986

A high resolution spatial and temporal multiple Doppler analysis of a microburst and its application to aircraft flight simulation

Multiple Doppler radar data collected during the Joint Airport Weather Studies (JAWS) Project is used to synthesize the three-dimensional wind in the region of a microburst. The particular microburst used in this study is the strongest one to date for which three-dimensional winds have been recovered. As a diagnostic tool, a six-DOF numerical aircraft model having characteristics similar to 727 series aircraft is used to investigate jet transport aircraft response to observed microburst winds during simulated approaches and departures. Simple pilot control laws are used to adjust thrust, pitch, roll, and yaw so as to maintain given approach or departure parameters. Generally, when horizontal wind shear along the approach or departure path is 0.01/s or greater, the model is unable to maintain the desired approach path and suffers a significant reduction in climb performance during a go-around or departure. Although the mean wind shear along a path gives a good qualitative measure of the wind shear threat to a jet transport, different paths with similar mean shears can yield markedly different results, as do the same paths through the microburst at different times. These findings are a direct consequence of the fine temporal and spatial scale of microburst winds. During any given modeled aircraft traverse through the region of highest horizontal shear, time variations in the microburst wind field are shown to have an insignificant effect on the modeled flight path. This is because the traverse period is short (30 s) compared to the lifetime of a microburst (300-600 s).

Elmore, K. L.↗

NASA NTRS1993

Long-lived artificial ion clouds in the earth's ionosphere

In two barium releases made over the Caribbean during the summer of 1991, the ion cloud was observed to last more than 10 hours. Observations were made with a low light level TV imager and a TV spectrograph operated onboard a Russian research vessel conducting ionospheric research and participating in the NASA-CRRES mission. The two clouds were observed near the release region for 15 to 25 minutes during the twilight following the initial release. One of the releases was made during evening twilight and the ion cloud reappeared the following morning, while the other was a morning release and the late-time observations made the next evening. The observations are highly surprising since, generally, it has been assumed that the ion cloud would dissipate within a few hours. However, the long life time appears consistent with current knowledge about dissipative processes. The long lifetime of barium ion clouds may provide for the most sensitive experimental testing of ionospheric convection models, a possibility with clear implications for future barium release experiments.

Milinevskij, G. P.↗

NASA NTRS1995

Reliability assessment of multiple quantum well avalanche photodiodes

The reliability of doped-barrier AlGaAs/GsAs multi-quantum well avalanche photodiodes fabricated by molecular beam epitaxy is investigated via accelerated life tests. Dark current and breakdown voltage were the parameters monitored. The activation energy of the degradation mechanism and median device lifetime were determined. Device failure probability as a function of time was computed using the lognormal model. Analysis using the electron beam induced current method revealed the degradation to be caused by ionic impurities or contamination in the passivation layer.

Yun, Ilgu↗

NASA NTRS2002

Detection by Transit Photometry

A periodic sequence of planetary transits provides a valid detection of an orbiting planet and provides the relative size of the planet and its orbital period. Ancillary measurements of the stellar spectrum and the variations of the star's radial velocity or position combined with stellar models allow the absolute size of the planet and its mass to be obtained. The results of this approach have already shown that the planet orbiting HD209458 has only 70% of the mass of Jupiter, but is nearly 50% larger in radius. Based on models of planetary structure, these results imply that the planet must have spent most of its lifetime so close to the star that it has not been able to cool and contract as have the giant planets in our Solar System. Thus its density is much less than Jupiter and Saturn and is actually less than that of water; i.e., about 0.4 gr/cu cm. If more sensitive measurements of the light curve of stars with closely orbiting planets can be made that provide the varying amplitude of the light reflected by the planet at various phases in its orbit, then characteristics of the planetary atmosphere can be obtained. Potentially, these data can identify major molecular species present in the atmosphere and tell us if clouds are present and yield the phase function of the aerosols. Although such detail cannot be obtained for Earth-size planets because their signal amplitudes are too small, it is possible to get data critical to the determination of the structure of extrasolar planetary systems. In particular, the size distributions and their orbital distributions can be measured by the transit photometry missions now in development. The COROT mission should be able to find large terrestrial planets in short-period orbits while the more ambitious Kepler and Eddington missions should be able to detect planets even smaller than the Earth and at orbital distances that place them in the habitable zone of their stars.

Borucki, William J.↗

NASA NTRS2003

Rapid Technology Assessment via Unified Deployment of Global Optical and Virtual Diagnostics

This paper discusses recent developments in rapid technology assessment resulting from an active collaboration between researchers at the Air Force Research Laboratory (AFRL) at Wright Patterson Air Force Base (WPAFB) and the NASA Langley Research Center (LaRC). This program targets the unified development and deployment of global measurement technologies coupled with a virtual diagnostic interface to enable the comparative evaluation of experimental and computational results. Continuing efforts focus on the development of seamless data translation methods to enable integration of data sets of disparate file format in a common platform. Results from a successful low-speed wind tunnel test at WPAFB in which global surface pressure distributions were acquired simultaneously with model deformation and geometry measurements are discussed and comparatively evaluated with numerical simulations. Intensity- and lifetime-based pressure-sensitive paint (PSP) and projection moire interferometry (PMI) results are presented within the context of rapid technology assessment to enable simulation-based R&D.

Jordan, Jeffrey D.↗

NASA NTRS2005

Results of a 2000 hour wear test of the NEXIS ion engine

The Nuclear Electric Xenon Ion System (NEXIS) ion thruster was developed for potential outer planet robotic missions under NASA's Prometheus program. This engine was designed to operate at power levels ranging from 16 to over 20 kWe at specific impulses of 6000 to 7500 s for burn times of up to 10 years, satisfying the requirements of nuclear electric propulsion systems such as that on the proposed Prometheus 1 mission to explore the icy moons of Jupiter. State-of-the-art performance and life assessment tools were used to design the thruster. Following the successful performance validation of a Laboratory Model thruster, Development Model hardware was fabricated and subjected to vibration and wear testing. The results of a 2000-hour wear test are reported herein. Thruster performance achieved the target requirements and was steady for the duration of the test. Ion optics performance was similarly stable. Discharge loss increases of 6 eV/ion were observed in the first 500 hours of the test and were attributed to primary electron energy decreases due to cathode insert conditioning. Relatively high recycle rates were observed and were identified to be high-voltage-to-ground arcs in the back of the thruster caused by wire insulation outgassing and electron penetration through the plasma screen. Field emission of electrons between the accelerator and screen grids was observed and attributed to evolution of field emitter sites at accelerator grid aperture edges caused by ion bombardment. Preliminary modeling and analysis indicates that the NEXIS engine can meet mission performance requirements over the required lifetime. Finally, successful validation of the NEXIS design methodology, design tools, and technologies with the results of the wear test and companion performance and vibration tests presents significant applicability of the NEXIS development effort to missions of near-term as well as long-term interest for NASA.

Nuclear Electric Xenon Ion System (NEXIS)Thruster ↗

NASA NTRS2005

Results of a 2000 Hour Wear Tof the NEXIS Ion Engine

Thruster performance↗

NASA NTRS2007

Spaceborne Autonomous and Ground Based Relative Orbit Control for the TerraSAR-X/TanDEM-X Formation

TerraSAR-X (TSX) and TanDEM-X (TDX) are two advanced synthetic aperture radar (SAR) satellites flying in formation. SAR interferometry allows a high resolution imaging of the Earth by processing SAR images obtained from two slightly different orbits. TSX operates as a repeat-pass interferometer in the first phase of its lifetime and will be supplemented after two years by TDX in order to produce digital elevation models (DEM) with unprecedented accuracy. Such a flying formation makes indeed possible a simultaneous interferometric data acquisition characterized by highly flexible baselines with range of variations between a few hundreds meters and several kilometers [1]. TSX has been successfully launched on the 15th of June, 2007. TDX is expected to be launched on the 31st of May, 2009. A safe and robust maintenance of the formation is based on the concept of relative eccentricity/inclination (e/i) vector separation whose efficiency has already been demonstrated during the Gravity Recovery and Climate Experiment (GRACE) [2]. Here, the satellite relative motion is parameterized by mean of relative orbit elements and the key idea is to align the relative eccentricity and inclination vectors to minimize the hazard of a collision. Previous studies have already shown the pertinence of this concept and have described the way of controlling the formation using an impulsive deterministic control law [3]. Despite the completely different relative orbit control requirements, the same approach can be applied to the TSX/TDX formation. The task of TDX is to maintain the close formation configuration by actively controlling its relative motion with respect to TSX, the leader of the formation. TDX must replicate the absolute orbit keeping maneuvers executed by TSX and also compensate the natural deviation of the relative e/i vectors. In fact the relative orbital elements of the formation tend to drift because of the secular non-keplerian perturbations acting on both satellites. The goal of the ground segment is thus to regularly correct this configuration by performing small orbit correction maneuvers on TDX. The ground station contacts are limited due to the geographic position of the station and the costs for contact time. Only with a polar ground station a contact visibility is possible every orbit for LEO satellites. TSX and TDX use only the Weilheim ground station (in the southern part of Germany) during routine operations. This station allows two scheduled contact per day for the nominal orbit configuration, meaning that the satellite conditions can be checked with an interval of 12 hours. While this limitation is usually not critical for single satellite operations, the visibility constraints drive the achievable orbit control accuracy for a LEO formation if a ground based approach is chosen. Along-track position uncertainties and maneuver execution errors affect the relative motion and can be compensated only after a ground station contact.

Ardaens, J. S.↗

NASA NTRS2012

A Fast and Efficient Version of the TwO-Moment Aerosol Sectional (TOMAS) Global Aerosol Microphysics Model

This study develops more computationally efficient versions of the TwO-Moment Aerosol Sectional (TOMAS) microphysics algorithms, collectively called Fast TOMAS. Several methods for speeding up the algorithm were attempted, but only reducing the number of size sections was adopted. Fast TOMAS models, coupled to the GISS GCM II-prime, require a new coagulation algorithm with less restrictive size resolution assumptions but only minor changes in other processes. Fast TOMAS models have been evaluated in a box model against analytical solutions of coagulation and condensation and in a 3-D model against the original TOMAS (TOMAS-30) model. Condensation and coagulation in the Fast TOMAS models agree well with the analytical solution but show slightly more bias than the TOMAS-30 box model. In the 3-D model, errors resulting from decreased size resolution in each process (i.e., emissions, cloud processing wet deposition, microphysics) are quantified in a series of model sensitivity simulations. Errors resulting from lower size resolution in condensation and coagulation, defined as the microphysics error, affect number and mass concentrations by only a few percent. The microphysics error in CN70CN100 (number concentrations of particles larger than 70100 nm diameter), proxies for cloud condensation nuclei, range from 5 to 5 in most regions. The largest errors are associated with decreasing the size resolution in the cloud processing wet deposition calculations, defined as cloud-processing error, and range from 20 to 15 in most regions for CN70CN100 concentrations. Overall, the Fast TOMAS models increase the computational speed by 2 to 3 times with only small numerical errors stemming from condensation and coagulation calculations when compared to TOMAS-30. The faster versions of the TOMAS model allow for the longer, multi-year simulations required to assess aerosol effects on cloud lifetime and precipitation.

Lee, Yunha↗