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DOE OSTI2025

Cold-Sprayed NMC622 Composite as a Cathode for Lithium-Ion Batteries

The growing demand for high-energy, low-cost lithium-ion batteries (LIBs) to power electric vehicles (EVs) necessitates advances in both materials and manufacturing processes. Conventional cathode fabrication methods, such as slurry casting and drying, are energy-intensive and pose challenges for scalability and environmental compliance. In this study, we propose cold-spray (CS) deposition as a solvent-free approach for fabricating LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) composite cathodes. Powder blends of NMC622, poly(vinylidene fluoride) (PVDF), and carbon black (CB) are directly deposited onto stainless steel and Inconel substrates under varied gas temperatures, pressures (and thus velocities), and standoff distances. The effects of temperature on the deposit morphology, coating density, and volume are systematically investigated. Computational fluid dynamics simulations reveal that increasing the gas temperature enhances the particle velocity, narrows the spray angle, and reduces the mass concentration radially at the nozzle outlet. CS deposition results in a dense cathode microstructure, accompanied by fracture in polycrystalline NMC622 particles. X-ray diffraction analysis further verifies that there are no phase changes during the deposition process. The electrochemical performance of the cold-sprayed cathodes reveals an initial capacity of approximately 96 mAh g –1 for single-crystal NMC622 and 167 mAh g –1 for polycrystalline NMC622. While these values are modest compared to state-of-the-art slurry-cast cathodes, which typically exhibit 180–200 mAh g –1 under optimized conditions. The results demonstrate a competitive performance given the solvent-free nature of the CS process and compare favorably with tape-cast samples made from identical feedstock. In conclusion, he CS process enables the formation of dense, binder-integrated cathode coatings without the need for solvent processing, offering a promising pathway for scalable, energy-efficient dry electrode manufacturing of next-generation LIBs.

Batteries↗

DOE OSTI2021

On Assessing ERA5 and MERRA2 Representations of Cold-Air Outbreaks Across the Gulf Stream

The warm Gulf Stream sea surface temperatures (SSTs) strongly impact the evolution of winter clouds behind atmospheric cold fronts. Such cloud evolution remains challenging to model. Here, the Gulf Stream is too wide within the ERA5 and MERRA2 reanalyses, affecting the turbulent surface fluxes. Known problems within the ERA5 boundary layer (too-dry and too-cool with too strong westerlies), ascertained primarily from ACTIVATE 2020 campaign aircraft dropsondes and secondarily from older buoy measurements, reinforce surface flux biases. In contrast, MERRA2 winter surface winds and air-sea temperature/humidity differences are slightly too weak, producing surface fluxes that are too low. Reanalyses boundary layer heights in the strongly-forced winter cold-air-outbreak regime are realistic, whereas late-summer quiescent stable boundary layers are too shallow. Nevertheless, the reanalysis biases are small, and reanalyses adequately support their use for initializing higher-resolution cloud process modeling studies of cold-air outbreaks.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2015

Sample Acquisition and Analytical Chemistry Challenges to Verifying Compliance to Aviators Breathing Oxygen (ABO) Purity Specification

NASA has been developing and testing two different types of oxygen separation systems. One type of oxygen separation system uses pressure swing technology, the other type uses a solid electrolyte electrochemical oxygen separation cell. Both development systems have been subjected to long term testing, and performance testing under a variety of environmental and operational conditions. Testing these two systems revealed that measuring the product purity of oxygen, and determining if an oxygen separation device meets Aviator's Breathing Oxygen (ABO) specifications is a subtle and sometimes difficult analytical chemistry job. Verifying product purity of cryogenically produced oxygen presents a different set of analytical chemistry challenges. This presentation will describe some of the sample acquisition and analytical chemistry challenges presented by verifying oxygen produced by an oxygen separator - and verifying oxygen produced by cryogenic separation processes. The primary contaminant that causes gas samples to fail to meet ABO requirements is water. The maximum amount of water vapor allowed is 7 ppmv. The principal challenge of verifying oxygen produced by an oxygen separator is that it is produced relatively slowly, and at comparatively low temperatures. A short term failure that occurs for just a few minutes in the course of a 1 week run could cause an entire tank to be rejected. Continuous monitoring of oxygen purity and water vapor could identify problems as soon as they occur. Long term oxygen separator tests were instrumented with an oxygen analyzer and with an hygrometer: a GE Moisture Monitor Series 35. This hygrometer uses an aluminum oxide sensor. The user's manual does not report this, but long term exposure to pure oxygen causes the aluminum oxide sensor head to bias dry. Oxygen product that exceeded the 7 ppm specification was improperly accepted, because the sensor had biased. The bias is permanent - exposure to air does not cause the sensor to return to its original response - but the bias can be accounted for by recalibrating the sensor. After this issue was found, continuous measurements of water vapor in the oxygen product were made using an FTIR. The FTIR cell is relatively large, so response time is slow - but moisture measurements were repeatable and accurate. Verifying ABO compliance for oxygen produced by commercial cryogenic processes has a different set of sample acquisition and analytical chemistry challenges. Customers want analytical chemists to conserve as much as possible. Hygrometers are not exposed to hours of continuous flow of oxygen, so they don't bias, but small amounts of contamination in valves can cause a "fail". K bottles are periodically cleaned and recertified - after cleaning residual moisture can cause a "fail". Operators let bottle pressure drop to room pressure, introduce outside air into the bottle, and the subsequent fill will "fail". Outside storage of K‐bottles has allowed enough in‐leakage, so contents will "fail".

Graf, John↗

NASA NTRS2022

Rapid Radiolytic Degradation of Amino Acids in the Martian Shallow Subsurface: Implications for the Search for Extinct Life

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of *1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just *20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.

Alexander A. Pavlov↗

NASA NTRS1977

The effect of outgassing upon the closure of cracks and the strength of lunar analogues

The effect of an ultrahigh vacuum and low water vapor pressure on the stress-strain relation in rocks was studied in order to understand geologic and tectonic processes of the moon. Terrestrial basaltic rocks carefully outgassed in high vacuum provided the sample material for the compression tests reported here. The tests were conducted either under 1 atm air saturated with moisture, or under high vacuum. Results of the stress-strain determinations indicated that the dry rocks could show as much as twice the strength of the wet rocks. The data may also provide a means of reconciling the high strength and high temperature exhibited by the lunar interior.

Mizutani, H.↗

NASA NTRS2012

Spark Ignition Characteristics of a LO2/LCH4 Engine at Altitude Conditions

The use of non-toxic propellants in future exploration vehicles would enable safer, more cost effective mission scenarios. One promising "green" alternative to existing hypergols is liquid methane/liquid oxygen. To demonstrate performance and prove feasibility of this propellant combination, a 100lbf LO2/LCH4 engine was developed and tested under the NASA Propulsion and Cryogenic Advanced Development (PCAD) project. Since high ignition energy is a perceived drawback of this propellant combination, a test program was performed to explore ignition performance and reliability versus delivered spark energy. The sensitivity of ignition to spark timing and repetition rate was also examined. Three different exciter units were used with the engine's augmented (torch) igniter. Propellant temperature was also varied within the liquid range. Captured waveforms indicated spark behavior in hot fire conditions was inconsistent compared to the well-behaved dry sparks (in quiescent, room air). The escalating pressure and flow environment increases spark impedance and may at some point compromise an exciter.s ability to deliver a spark. Reduced spark energies of these sparks result in more erratic ignitions and adversely affect ignition probability. The timing of the sparks relative to the pressure/flow conditions also impacted the probability of ignition. Sparks occurring early in the flow could trigger ignition with energies as low as 1-6mJ, though multiple, similarly timed sparks of 55-75mJ were required for reliable ignition. An optimum time interval for spark application and ignition coincided with propellant introduction to the igniter and engine. Shifts of ignition timing were manifested by changes in the characteristics of the resulting ignition.

Kleinhenz, Julie↗

NASA NTRS1981

Development of Advanced Czochralski Growth Process to produce low cost 150 KG silicon ingots from a single crucible for technology readiness

The modified CG2000 crystal grower construction, installation, and machine check-out was completed. The process development check-out proceeded with several dry runs and one growth run. Several machine calibrations and functional problems were discovered and corrected. Several exhaust gas analysis system alternatives were evaluated and an integrated system approved and ordered. A contract presentation was made at the Project Integration Meeting at JPL, including cost-projections using contract projected throughput and machine parameters. Several growth runs on a development CG200 RC grower show that complete neck, crown, and body automated growth can be achieved with only one operator input. Work continued for melt level, melt temperature, and diameter sensor development.

Source record↗

NASA NTRS2012

Spark Ignition Characteristics of a L02/LCH4 Engine at Altitude Conditions

The use of non-toxic propellants in future exploration vehicles would enable safer, more cost effective mission scenarios. One promising "green" alternative to existing hypergols is liquid methane/liquid oxygen. To demonstrate performance and prove feasibility of this propellant combination, a 100lbf LO2/LCH4 engine was developed and tested under the NASA Propulsion and Cryogenic Advanced Development (PCAD) project. Since high ignition energy is a perceived drawback of this propellant combination, a test program was performed to explore ignition performance and reliability versus delivered spark energy. The sensitivity of ignition to spark timing and repetition rate was also examined. Three different exciter units were used with the engine s augmented (torch) igniter. Propellant temperature was also varied within the liquid range. Captured waveforms indicated spark behavior in hot fire conditions was inconsistent compared to the well-behaved dry sparks (in quiescent, room air). The escalating pressure and flow environment increases spark impedance and may at some point compromise an exciter s ability to deliver a spark. Reduced spark energies of these sparks result in more erratic ignitions and adversely affect ignition probability. The timing of the sparks relative to the pressure/flow conditions also impacted the probability of ignition. Sparks occurring early in the flow could trigger ignition with energies as low as 1-6mJ, though multiple, similarly timed sparks of 55-75mJ were required for reliable ignition. An optimum time interval for spark application and ignition coincided with propellant introduction to the igniter and engine. Shifts of ignition timing were manifested by changes in the characteristics of the resulting ignition.

Kleinhenz, Julie↗

NASA NTRS2016

Sorbent Structural Testing on Carbon Dioxide Removal Sorbents for Advanced Exploration Systems

Long term space missions require carbon dioxide removal systems that can function with minimal downtime required for maintenance, low power consumption and maximum efficiency for CO2 removal. A major component of such a system are the sorbents used for the CO2 and desiccant beds. Sorbents must not only have adequate CO2 and H2O removal properties, but they must have the mechanical strength to prevent structural breakdown due to pressure and temperature changes during operation and regeneration, as well as resistance to breakdown due to moisture in the system from cabin air. As part of the studies used to select future CO2 sorbent materials, mechanical tests are performed on various zeolite sorbents to determine mechanical performance while dry and at various humidified states. Tests include single pellet crush, bulk crush and attrition tests. We have established a protocol for testing sorbents under dry and humid conditions, and previously tested the sorbents used on the International Space Station carbon dioxide removal assembly. This paper reports on the testing of a series of commercial sorbents considered as candidates for use on future exploration missions.

Watson, David↗

NASA NTRS1992

The gabbro-eclogite phase transition and the elevation of mountain belts on Venus

Among the four mountain belts surrounding Lakshmi Planum, Maxwell Montes is the highest and stands up to 11 km above the mean planetary radius and 7 km above Lakshmi Planum. The bulk composition and radioactive heat production of the crust on Venus, where measured, are similar to those of terrestrial tholeiitic basalt. Because the thickness of the low-density crust may be limited by the gabbro-garnet granulite-eclogite phase transitions, the 7-11 km maximum elevation of Maxwell Montes is difficult to understand except in the unlikely situation that the crust contains a large volume of magma. A possible explanation is that the base of the crust is not in phase equilibrium. It has been suggested that under completely dry conditions, the gabbro-eclogite phase transition takes place by solid-state diffusion and may require a geologically significant time to run to completion. Solid-state diffusion is a strongly temperature-dependent process. In this paper we solve the thermal evolution of the mountain belt to attempt to constrain the depth of the gabbro-eclogite transition and thus to assess this hypothesis quantitatively. The one-dimensional heat equation is solved numerically by a finite difference approximation. The deformation of the horizontally shortening crustal and mantle portions of the thermal boundary layer is assumed to occur by pure shear, and therefore the vertical velocity is given by the product of the horizontal strain rate and depth.

Namiki, Noriyuki↗

NASA NTRS1995

Growth of single crystals of organic salts with large second-order optical nonlinearities by solution processes for devices

Data obtained from the electric field induced second harmonic generation (EFISH) and Kurtz Powder Methods will be provided to MSFC for further refinement of their method. A theoretical model for predicting the second-order nonlinearities of organic salts is being worked on. Another task is the synthesis of a number of salts with various counterions. Several salts with promising SHG activities and new salts will be tested for the presence of two crystalline forms. The materials will be recrystallized from dry and wet solvents and compared for SHG efficiency. Salts that have a high SHG efficiency and no tendency to form hydrates will be documented. The synthesis of these materials are included in this report. A third task involves method to aid in the growth of large, high quality single crystals by solution processes. These crystals will be characterized for their applicability in the fabrication of devices that will be incorporated into optical computers in future programs. Single crystals of optimum quality may be obtained by crystal growth in low-gravity. The final task is the design of a temperature lowering single crystal growth apparatus for ground based work. At least one prototype will be built.

Leslie, Thomas M.↗

NASA NTRS1998

Flashback Arrestor for LPP, Low NOx Combustors

Lean premixed, prevaporized (LPP) high temperature combustor designs as explored for the Advanced Subsonic Transport (AST) and High Speed Civil Transport (HSCT) combustors can achieve low NO(x), emission levels. An enabling device is needed to arrest flashback and inhibit preignition at high power conditions and during transients (surge and rapid spool down). A novel flashback arrestor design has demonstrated the ability to arrest flashback and inhibit preignition in a 4.6 cm diameter tubular reactor at full power inlet temperatures (725 C) using Jet-A fuel at 0.4 less than or equal To phi less than or equal to 3.5. Several low pressure loss (0.2 to 0.4% at 30 m/s) flashback arrestor designs were developed which arrested flashback at all of the test conditions. Flame holding was also inhibited off the flash arrestor face or within the downstream tube even velocities (less than or equal to 3 to 6 m/s), thus protecting the flashback arrestor and combustor components. Upstream flow conditions influence the specific configuration based on using either a 45% or 76% upstream geometric blockage. Stationary, lean premixed dry low NO(x) gas turbine combustors would also benefit from this low pressure drop flashback arrestor design which can be easily integrated into new and existing designs.

Kraemer, Gil↗

NASA NTRS2013

Miniature Sensor Probe for O2, CO2, and H2O Monitoring in Portable Life Support Systems

A miniature sensor probe, composed of four sensors which monitor the partial pressure of O2, CO2, H2O, and temperature, designed to operate in the portable life support system (PLSS), has been demonstrated. The probe provides an important advantage over existing technology in that it is able to operate reliably while wet. These luminescence-based fiber optic sensors consist of an indicator chemistry immobilized in a polymeric film, whose emission lifetime undergoes a strong change upon a reversible interaction with the target gas. Each sensor includes chemistry specifically sensitive to one target parameter. All four sensors are based on indicator chemistries that include luminescent dyes from the same chemical family, and therefore exhibit similar photochemical properties, which allow performing measurements of all the sensors by a single, compact, low-power optoelectronic unit remotely connected to the sensors by an electromagnetic interference-proof optical fiber cable. For space systems, using these miniature sensor elements with remote optoelectronics provides unmatched design flexibility for measurements in highly constrained volume systems such as the PLSS. A 10 mm diameter and 15 mm length prototype multiparameter probe was designed, fabricated, tested, and demonstrated over a wide operational range of gas concentration, humidity, and temperature relevant to operation in the PLSS. The sensors were evaluated for measurement range, precision, accuracy, and response time in temperatures ranging from 50 aF-150 aF and relative humidity from dry to 100% RH. Operation of the sensors in water condensation conditions was demonstrated wherein the sensors not only tolerated liquid water but actually operated while wet.

Delgado, Jesus↗

DOE OSTI2024

Microwave-Assisted Syngas Cleanup: Catalytic Reforming of Gasifier Tar Using a Low-Cost Iron Catalyst

The microwave-assisted gasification of plastic wastes to produce hydrogen-rich syngas is an attractive energy-saving plastic upcycling route, and the addition of biomass could improve the quality of the syngas produced; however, it could also increase the tar yield, which is an undesired, secondary product in this process. The presence of tars could result in downstream lines blockage, reactor down time and costly maintenance. Therefore, reducing or removing tar is desired. Due to its chemical complexity, toluene, which is one of the main tar constituents, could be used as a model tar compound. In this work, the microwave-assisted catalytic dry reforming of toluene was studied using Fe/Al2O3 as a catalyst, under CO2 at different reaction temperatures. The toluene reforming reaction was conducted using microwave and conventional thermal reactors. The results showed that under microwave irradiation, higher CO2 and toluene conversions, as well as better hydrogen yield can be observed compared to conventional toluene reforming at the same reaction temperature. The catalyst stability test was also investigated. Three reaction pathways were observed during microwave reaction.

Bai, Xinwei↗

NASA NTRS2010

Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

Polyimide aerogels with three-dimensional cross-linked structure are made using linear oligomeric segments of polyimide, and linked with one of the following into a 3D structure: trifunctional aliphatic or aromatic amines, latent reactive end caps such as nadic anhydride or phenylethynylphenyl amine, and silica or silsesquioxane cage structures decorated with amine. Drying the gels supercritically maintains the solid structure of the gel, creating a polyimide aerogel with improved mechanical properties over linear polyimide aerogels. Lightweight, low-density structures are desired for acoustic and thermal insulation for aerospace structures, habitats, astronaut equipment, and aeronautic applications. Aerogels are a unique material for providing such properties because of their extremely low density and small pore sizes. However, plain silica aerogels are brittle. Reinforcing the aerogel structure with a polymer (X-Aerogel) provides vast improvements in strength while maintaining low density and pore structure. However, degradation of polymers used in cross-linking tends to limit use temperatures to below 150 C. Organic aerogels made from linear polyimide have been demonstrated, but gels shrink substantially during supercritical fluid extraction and may have lower use temperature due to lower glass transition temperatures. The purpose of this innovation is to raise the glass transition temperature of all organic polyimide aerogel by use of tri-, tetra-, or poly-functional units in the structure to create a 3D covalently bonded network. Such cross-linked polyimides typically have higher glass transition temperatures in excess of 300 400 C. In addition, the reinforcement provided by a 3D network should improve mechanical stability, and prevent shrinkage on supercritical fluid extraction. The use of tri-functional aromatic or aliphatic amine groups in the polyimide backbone will provide such a 3D structure.

Panek, John↗

DOE OSTI2025

Evaluating indoor thermal resilience of passive and low-power cooling shelters for outdoor workers in India

India’s 231 million outdoor workers are exposed to deadly heat during heat waves. We report results from a simulation-based study that focuses on passive design of cooling shelters for the hot and dry climate zone of India. The goal is to design a cooler-than-outdoor shelter for outdoor workers’ intermittent rest and recovery from heat stress during their arduous outdoor work, to avoid heat-related morbidities and mortality. Expected indoor thermal conditions in low-cost cooling shelters deploying a range of passive designs and low-power active measures are investigated, consistent with the current Indian standards and practices, located in the city of Jodhpur in western India. Heat resilience of the shelter was measured with the predicted reduction of hazardous hours inside the shelter based on the wet-bulb globe temperature (WBGT) and extended heat index. These measures include improving the building envelope, installing cool roofs, using internal thermal mass, and natural ventilation. Additionally, a low-power active measure of using ventilation fans and ceiling fans is explored. EnergyPlus-based simulation results show that simple, commonly available measures, particularly natural ventilation and ceiling fans, achieve the most significant reductions in overheating danger hours, by 22% and 21%, respectively, while more complex or costly passive strategies yield only marginal additional benefits. Moreover, combined measure packages are identified that can reduce the indoor WBGT by 8 to 10 °C, eliminating overheating danger hours. These findings highlight the critical importance of scalable, low-cost, and easily deployable cooling solutions for developing resilient cooling shelters for vulnerable outdoor workers during heat waves in India.

building performance↗

NASA NTRS1996

Dehydration of the Upper Troposphere and Lower Stratosphere by Subvisible Cirrus Clouds Near the Tropical Tropopause

The extreme dryness of the lower stratosphere is believed to be caused by freeze-drying of air as it enters the stratosphere through the cold tropical tropopause. Previous investigations have been focused on dehydration occurring at the tops of deep convective cloud systems, However, recent observations of a ubiquitous stratiform cirrus cloud layer near the tropical tropopause suggest the possibility of dehydration as air is slowly lifted by large-scale motions, In this study, we have evaluated this possibility using a detailed ice cloud model. Simulations of ice cloud formation in the temperature minima of gravity waves (wave periods of 1 - 2 hours) indicate that large numbers of ice crystals will likely form due to the low temperatures and rapid cooling. As a result, the crystals do not grow larger than about 10 microns, fallspeeds are no greater than a few cm/s, and little or no precipitation or dehydration occurs. However, ice cloud's formed by large-scale vertical motions (with lifetimes of a day or more) should have,fever crystals and more time for crystal sedimentation to occur, resulting in water vapor depletions as large as 1 ppmv near the tropopause. We suggest that gradual lifting near the tropical tropopause, accompanied by formation of thin cirrus, may account for the dehydration.

Jensen, Eric J.↗

DOE OSTI2026

The evolution of coal porosity during pyrolysis

Gasification of coal, municipal waste, or other organic materials is a potential hydrogen source that entails complex thermal decomposition and transport processes. This study provides a multiscale analysis of these processes for sub-bituminous (Usibelli, Healy, Alaska) and lignite (Center, North Dakota) coals and provides data useful for process design. The chemistry, mineralogy, and pore structures of pyrolyzed coal and their evolution with thermal decomposition are discussed. Samples pyrolyzed at 200–1000 °C were analyzed by small-angle neutron scattering; ultra-small, small-, and wide-angle X-ray scattering; and other complementary techniques. Scanning electron microscopy showed new pores in the high-temperature-pyrolyzed material. Upon heating, the coals became progressively denser, and the concentration of hydrogen decreased. Changes in pore volume fell into three temperature ranges: an initial, low-temperature range that, for the Usibelli coal, involved an increase in overall porosity; a mid-temperature range associated with pore volume loss; and a high-temperature range associated with significant porosity increase and char formation. This transformation was paralleled by changes in fractal dimension and correlation length. The higher the pyrolysis temperature the greater the small-pore-volume fraction and overall surface area became. Pyrolysis increased the lateral size of coal crystallites, decreased the amorphous fraction, and increased the aromatics fraction and overall coal rank. Comparisons of neutron and X-ray scattering data and subsequent water uptake studies showed that pre-dried coals can re-hydrate relatively rapidly upon exposure to air, which can significantly affect the porosity calculated from small-angle-scattering data. Fits to the cumulative porosity curves provide a method for modeling the physical and chemical transformation of hydrogen-containing feedstock during gasification.

Anovitz, Lawrence {Larry} [ORNL] (ORCID:0000000226↗