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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Elucidating the Redox Behavior during Atomic Layer Deposition on Lithium-Ion Battery Cathode Materials

Atomic layer deposition (ALD) has emerged as a promising technology for applying ultrathin protective coatings on lithium-ion battery (LIB) cathode surfaces to improve their cycling stability. While there have been numerous reports evaluating the electrochemical performance of these surface-modified cathode materials, the chemical changes induced on the surface of the cathode materials upon ALD coating are not fully studied. This paper describes a systematic investigation to understand the interfacial changes of 12 different cathode materials upon coating with aluminum oxide (Al 2 O 3 ) using trimethyl aluminum (TMA) and H 2 O, and aluminum fluoride (AlF 3 ) using TMA and hydrogen fluoride pyridine (HFPy). Here, the surface composition of these cathode materials, which range from simple transition metal oxides (e.g. NiO and MnO) to complex multi-element cathode materials (e.g. LiNi x Mn 1-x-y Co y O 2 , NMC), was studied via X-ray photoelectron spectroscopy (XPS). The XPS measurements reveal that the transition metals in the cathode materials undergo selective oxidation/reduction depending upon the nature of the precursor, the coating, and the cathode material. The ability to chemically modify the surface of cathode materials via vapor-phase precursor adsorption will open new avenues to systematically control the interface of the cathode materials in LIBs that are not possible by conventional coating methods.

25 ENERGY STORAGE↗
DOE OSTI2025

Porogen‐Integrated Rapid Oxidation Enables Structured Mesoporous Metal Oxide Films

Structured metal oxide films have promise in optoelectronics, sensing, energy storage, and catalysis but their uptake is predominately limited due to their long and high‐temperature syntheses. Here, in this study, a self‐assembling polymer is used which can act as a chelating fuel source in a solution combustion reaction to generate highly structured mesoporous aluminum oxide films at <250 °C in a matter of minutes through a process termed porogen‐integrated rapid oxidation (PiRO). The resulting films with thicknesses up to 500 nm show an open‐cell, face‐centered cubic structure of spheroidal pores. Further, an additional ligand can be included to control the self‐assembly step to yield both through‐film ordering or tunable disordering for increased pore volume as confirmed by both grazing incidence small angle X‐ray scattering and ellipsometry. Finally, roll‐to‐roll manufacturing with PiRO is demonstrated on flexible polymeric substrates. The method offers a tunable, scalable, low‐temperature, and lower‐cost method to generate large‐area structured mesoporous metal oxide films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

An Integrated Flame Spray Process for Low Cost Production of Battery Materials for Lithium Ion Batteries and Beyond

The overall objective of this project was to develop an advanced manufacturing technology for Li-ion battery materials production at low cost and in a green chemical process using glycerol as solvent to replace water. It was aimed at developing a prototype pilot production line to reduce production cost by at least 25% to the baseline. During the course of this project, research was conducted to understand spray drying and combustion of eutectic solvent precursors of glycerol and metal salts (acetates) in the formation of mixed metal oxide powders. Reactor design and optimization were done to facilitate spray drying and combustion in powder formation and processing. Various cathode materials powders were produced, including lithium nickel-cobalt-manganese oxide (NCM) and lithium nickel-cobalt-aluminum oxide (NCA). These cathode materials powders were tested in half coin cells for their performances, with materials performances of 160 mAh/g for NCM111 and 200 mAh/g for NCA. NCA powders were also produced using a slurry spray-drying process and tested in full pouch cells. A pilot scale flame assisted spray drying reactor was constructed and demonstrated for its production rate exceeding the target of production rate of four metric tons per year. The work performed in this project has been documented in 9 peer reviewed journal publications, 8 conference presentations, and two IP disclosures/patent applications.

25 ENERGY STORAGE↗
NASA NTRS1973

Investigation of substrate-mounted thin-film meteoroid sensors for use in large area impact experiments

Two types of sensor designs were investigated: (1)a polysulfone dielectric film with vapor-deposited aluminum and gold sensor plates, bonded to a relatively thick aluminum substrate, and (2) an aluminum oxide (A1203) dielectric layer prepared on an aluminum substrate by anodization, with a layer of vapor-deposited aluminum providing one sensor plate and the substrate serving as the other plate. In the first design, specimens were prepared which indicate the state of the art for application of this type of sensor for elements of a meteoroid detection system having an area as large as 10 sq M. Techniques were investigated for casting large-area polysulfone films on the surface of water and for transferring the films from the water. Methods of preparing sensors by layering of films, the deposition of capacitor plates, and sensor film-to-substrate bonding, as well as techniques for making electrical connections to the capacitor plates, were studied.

Carollo, S. F.↗
NASA NTRS1978

Electrically conductive thermal control coatings

A coating characterized by low thermal absorption, high thermal emittance and high electrical conductivity comprises: (1) a fired oxide pigment comprising a minor amount of aluminum oxide and a major amount of zinc oxide; (2) sufficient water to provide a mixture suitable for application to a substrate, is presented. The fired oxide pigment may further include a minor amount of cobalt oxide. The resulting coating is particularly useful for coating the surfaces of spacecraft and similar objects.

Shai, M. C.↗
NASA NTRS1986

Ester oxidation on an aluminum surface using chemiluminescence

The oxidation characteristics of a pure ester (trimethyolpropane triheptanoate) were studied by using a chemiluminescence technique. Tests were run in a thin film microoxidation apparatus with an aluminum alloy catalyst. Conditions included a pure oxygen atmosphere and a temperature range of 176 to 206 C. Results indicated that oxidation of the ester (containing .001 M diphenylanthracene as an intensifier) was accompanied by emission of light. The maximum intensity of light emission was a function of the amount of ester, the concentration of intensifier, and the test temperature. The induction period, or the time to reach one-half of maximum intensity was inversely proportional to test temperature. Decreases in light emission at the later stages of a test were caused by depletion of the intensifier.

Jones, William R., Jr.↗
DOE OSTI2020

Ultradense Arrays of Sub-100 nm Co/CoO Nanodisks for Spintronics Applications

Sub-100 nm ferromagnetic/antiferromagnetic nanodisks present enhanced magnetic properties with respect to their thin film counterparts. Co/CoO disks were fabricated over large areas by a transferring process of an anodic aluminum oxide membrane, electron beam evaporation of Co, and subsequent oxidation to CoO. This method reveals exchange bias fields up to 4 times larger than that in thin films and higher blocking temperatures for the same oxidation protocol. The significant improvement of the magnetic properties is attributed to finite-size effects in nanostructures and might be exploited in diverse areas such as the magnetic stabilization of ultradense arrays or the scalability process of patterned heterostructures in spintronic phenomena.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Identifying native point defect configurations in α-alumina

Intimately intertwined atomic and electronic structures of point defects govern diffusion-limited corrosion and underpin the operation of optoelectronic devices. For some materials, complex energy landscapes containing metastable defect configurations challenge first-principles modeling efforts. Here, we thoroughly reevaluate native point defect geometries for the illustrative case of α-Al 2 O 3 by comparing three methods for sampling candidate geometries in density functional theory calculations: displacing atoms near a naively placed defect, initializing interstitials at high-symmetry points of a Voronoi decomposition, and Bayesian optimization. We find symmetry-breaking distortions for oxygen vacancies in some charge states, and we identify several distinct oxygen split-interstitial geometries that help explain literature discrepancies involving this defect. We also report a surprising and, to our knowledge, previously unknown trigonal geometry favored by aluminum interstitials in some charge states. Importantly, these new configurations may have transformative impacts on our understanding of defect migration pathways in aluminum-oxide scales protecting metal alloys from corrosion. Overall, the Voronoi scheme appears most effective for sampling candidate interstitial sites because it always succeeded in finding the lowest-energy geometry identified in this study, although no approach found every metastable configuration. Finally, we show that the position of defect levels within the band gap can depend strongly on the defect geometry, underscoring the need to conduct careful searches for ground-state geometries in defect calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Laser-Induced Trapping of Metastable Amorphous AlO x /C (2.5 < x ≤ 3.5) Nanocomposites: Implications for Use as Solid Phase Gas Generators

The synthesis of kinetically "frozen" metastable nanostructures remains elusive. This limitation has severely restricted the current paradigms in materials discovery. We overcame this challenge by phase-stabilizing unusually hyperoxidized and metastable amorphous aluminum oxide (a-AlO x ; 2.5 < x ≤ 3.5) nanostructures. Specifically, we employed laser ablation synthesis in solution (LASiS) as a one-pot nonequilibrium technique to achieve this pivotal advancement. Structural and compositional characterizations of the as-synthesized material reveal highly disordered a-AlO x nanoparticles that are remarkably stabilized by interfacial monolayers of ordered carbon atoms. Both structure and chemical composition were confirmed with disparate characterization methods at different length scales. The nanoparticles of sizes less than10 nm were stable even at elevated temperatures. Only at temperatures higher than 750 °C do the a-AlO x structures undergo a solid-solid phase transition that culminates in the formation of stable α-Al 2 O 3 while releasing excess trapped gases. In conclusion, such disruptive materials can find applications in emerging technologies seeking metastable phase-change materials for solid phase gas generators, batteries, neuromorphic computing, and energetic additives.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Thermoluminescence and optically stimulated luminescence response of Al 2 O 3 coatings deposited by mist-chemical vapor deposition

Aluminum oxide (Al 2 O 3 ) is a widely used ceramic material which can be applied as a protective coating on metallic structures to improve corrosion resistance and mechanical properties. Al 2 O 3 also has great potential as a functional thin film device in optoelectronics. When it is doped with carbon (Al 2 O 3 :C), this material system can serve as a reliable radiation dosimeter. The combination of optoelectronic, dosimetric, and protective properties demonstrated by Al 2 O 3 uniquely positions it for dual use applications in nuclear forensics, nonproliferation and safeguards, emergency response, retrospective dosimetry, and nondestructive inspection. Here, in this study, an innovative ultrasonic mist-chemical vapor deposition (Mist-CVD) system was used to deposit thin (nm level) Al 2 O 3 coatings on 304 stainless steel substrates. The single aliquot regeneration (SAR) and additive dose reconstruction techniques were then used to investigate the thermoluminescence (TL) and optically stimulated luminescence (OSL) response of the coated substrates to increasing doses of β irradiation. This study demonstrates that nm-thick Al 2 O 3 coatings hold promise as novel nano-dosimeters which could be leveraged for a series of applications such as nonproliferation and safeguards, retrospective dosimetry, and nondestructive inspection.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Review and Summary of Corrosion Behavior for Aluminum-Clad Spent Nuclear Fuel in Dry Storage

A description of the corrosion behavior of aluminum alloys used for cladding on aluminum-based, aluminum-clad nuclear fuel used in research reactors under potential dry storage conditions has been compiled. An evaluation is made of potential additional corrosion with water postulated to not be removed during drying. The relative humidity (RH) produced by typical dryness criteria for industrial spent nuclear fuel drying is expected to be low, particularly at high temperatures (17% RH at 20°C and lower at higher temperatures). Existing corrosion data suggests that negligible vapor-phase corrosion of aluminum is expected at such low humidity, even for nominally bare aluminum surfaces. That is, the predicted relative humidity from free water (e.g., 17% RH) is below the “critical” relative humidity (~40% RH at room temperature), below which no significant corrosion is observed for bare aluminum. Furthermore, reported room-temperature corrosion rates are very low even under saturated (100% RH) water vapor. Existing results showing significant vapor-phase corrosion corresponded specifically to conditions of high temper ed with high relative humidity. A relatively large reservoir of (chemically bound) water exists in the aluminum (oxy)hydroxide films on the SNF cladding surface. The estimated total could saturate the gas even at relatively high temperature if fully released; however, its release as molecular water is expected to only be plausible if the temperature during storage exceeds both the drying temperature and the threshold for thermal decomposition of the trihydroxides (~220°C). Therefore, the combination of high temperature and high relative humidity that could drive significant corrosion is considered implausible during sealed dry storage following an appropriate drying process, to include >220°C drying for canisters that may approach or exceed this temperature during storage. Vapor-phase testing of aluminum samples with an adherent (oxy)hydroxide layer, prepared in liquid water to resemble those on actual aluminum-clad spent nuclear fuel (ASNF), did not observe evidence of additional corrosion even at combined high-temperature (up to 180°C) and high-humidity (up to 100% RH) conditions. Instead, small net mass losses were observed for most specimens and attributed to dehydration of the samples, which had been air-dried only prior to testing. ASNF being moved to dry storage is expected to have an existing (oxy)hydroxide film, suggesting that the cladding will be less prone to additional corrosion than bare aluminum metal. If significant corrosion did occur during sealed storage, the overall extent and impact is expected to be small. Corrosion post-closure of a canister would not alter the total amount of hydrogen in the canister, so it would have no effect on the maximum H 2 release already assessed in existing bounding calculations. In addition, the total amount of water in a 25-µm dense bayerite film would consume a only ~8 µm additional aluminum metal on average, if fully consumed by oxidizing aluminum metal to Al 2 O 3 . These conclusions are consistent with ASNF-in-canister simulations to date, which included a reaction pathway for corrosion using kinetics from previous literature and believed to be conservative and predicted very low rates of corrosion.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1984

Behavior of plasma-sprayed coatings

The microstructural development of plasma sprayed oxide coatings is described with particualr reference to aluminum oxide coatings and thermal barrier coatings of yttria stabilized zirconia (YSZ). The microstructural features of these coatings, observed by optical and electron microscopy, are related to their mechanical behavior. The adhesion of the coatings is also investigated using fracture toughness and tensile tests. It is noted that acoustic emission is valuable in formulating possible fracture mechanisms for YSZ coatings.

Berndt, Christopher C.↗
DOE OSTI2025

Off-state magnetoresistance in long-channel germanium Schottky-barrier MOSFETs

An increasing magnetic field perpendicular to an undoped semiconductor surface at low temperature is known to strengthen the binding of localized electrons to stationary ions, as the wavefunction's tails evolve from exponential to Gaussian. It is also known that application of a high bias voltage to a depleted semiconductor can liberate bound charge and induce a large drop in electrical resistance. We connect these established results to experimental electrical transport measurements on off-state germanium Schottky-barrier metal–oxide–semiconductor field-effect transistor (MOSFETs) with an aluminum oxide insulating dielectric and platinum germanide contacts. We make measurements at the three distinct orientations of the magnetic field with respect to the substrate and the current. At 6 K, we observe sharp attenuation of current by more than 2 orders of magnitude, within 60 mT, at a crossover magnetic field perpendicular to the substrate. A 1 T magnetic field attenuates the current by more than 4 orders of magnitude. The strength of the attenuation and the value of the crossover field are controlled by both the gate–source and drain–source voltages. The attenuation is much weaker when the magnetic field is parallel to the current. Finally, we orient the magnetic field parallel to the substrate, but perpendicular to the current, allowing us to distinguish charge hopping at the oxide interface from charge hopping in the bulk. In conclusion, this large off-state magnetoresistance can be exploited for cryogenic magnetic- and photo-detection, and for high-bias, low-leakage MOSFETs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
NASA NTRS1975

Nitric oxide, water vapor, and ozone in the atmosphere as measured in SITU from an aircraft

As part of the instrument evaluation plan for the NASA Global Atmospheric Sampling Program, prototype instruments were tested aboard the NASA Convair 990 during four flights in January and February of 1974. All the data were taken in maritime air between Hawaii and San Francisco and between Hawaii and 155 deg W, 35 deg N. A chemiluminescent instrument was used to measure nitric oxide. Water vapor, which was measured by using an aluminum oxide hygrometer, ranged from 5.2 micro g/g to saturation. Ozone was measured by an instrument using the ultraviolet absorption technique and ranged up to 235 ppbv. Typical temporal plots of the concentrations of the three constituents are presented. All the constituents showed considerable spatial and day-to-day variation in concentration at each altitude flown. Measurements of the three constituents were made simultaneously at various altitudes between 7.6 and 12.5 km.

Briehl, D.↗
NASA NTRS1990

Thermal control system corrosion study

During the development of an expert system for autonomous control of the Space Station Thermal Control System (TCS), the thermal performance of the Brassboard TCS began to gradually degrade. This degradation was due to filter clogging by metallic residue. A study was initiated to determine the source of the residue and the basic cause of the corrosion. The investigation focused on the TCS design, materials compatibility, Ames operating and maintenance procedures, and chemical analysis of the residue and of the anhydrous ammonia used as the principal refrigerant. It was concluded that the corrosion mechanisms involved two processes: the reaction of water alone with large, untreated aluminum parts in a high pH environment and the presence of chlorides and chloride salts. These salts will attack the aluminum oxide layer and may enable galvanic corrosion between the aluminum and the more noble stainless steel and other metallic elements present. Recommendations are made for modifications to the system design, the materials used, and the operating and maintenance procedures, which should largely prevent the recurrence of these corrosion mechanisms.

Yee, Robert↗
NASA NTRS2012

Mars Aqueous Processing System

The goal of the Mars Aqueous Processing System (MAPS) is to establish a flexible process that generates multiple products that are useful for human habitation. Selectively extracting useful components into an aqueous solution, and then sequentially recovering individual constituents, can obtain a suite of refined or semi-refined products. Similarities in the bulk composition (although not necessarily of the mineralogy) of Martian and Lunar soils potentially make MAPS widely applicable. Similar process steps can be conducted on both Mars and Lunar soils while tailoring the reaction extents and recoveries to the specifics of each location. The MAPS closed-loop process selectively extracts, and then recovers, constituents from soils using acids and bases. The emphasis on Mars involves the production of useful materials such as iron, silica, alumina, magnesia, and concrete with recovery of oxygen as a byproduct. On the Moon, similar chemistry is applied with emphasis on oxygen production. This innovation has been demonstrated to produce high-grade materials, such as metallic iron, aluminum oxide, magnesium oxide, and calcium oxide, from lunar and Martian soil simulants. Most of the target products exhibited purities of 80 to 90 percent or more, allowing direct use for many potential applications. Up to one-fourth of the feed soil mass was converted to metal, metal oxide, and oxygen products. The soil residue contained elevated silica content, allowing for potential additional refining and extraction for recovery of materials needed for photovoltaic, semiconductor, and glass applications. A high-grade iron oxide concentrate derived from lunar soil simulant was used to produce a metallic iron component using a novel, combined hydrogen reduction/metal sintering technique. The part was subsequently machined and found to be structurally sound. The behavior of the lunar-simulant-derived iron product was very similar to that produced using the same methods on a Michigan iron ore concentrate, which demonstrates that lunar-derived material can be used in a manner similar to conventional terrestrial iron. Metallic iron was also produced from the Mars soil simulant. The aluminum and magnesium oxide products produced by MAPS from lunar and Mars soil simulants exhibited excellent thermal stability, and were shown to be capable of use for refractory oxide structural materials, or insulation at temperatures far in excess of what could be achieved using unrefined soils. These materials exhibited the refractory characteristics needed to support iron casting and forming operations, as well as other thermal processing needs. Extraction residue samples contained up to 79 percent silica. Such samples were successfully fused into a glass that exhibited high light transmittance.

Berggren, Mark↗