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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Chemical Environment and Structural Variations in High Entropy Oxide Thin Film Probed with Electron Microscopy

For this work, we employ analytical transmission electron microscopy (TEM) to correlate the structural and chemical environment variations within a stacked epitaxial thin film of the high entropy oxide (HEO) Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 O (J14), with two layers grown at different substrate temperatures (500 and 200 °C) using pulsed laser deposition (PLD). Electron diffraction and atomically resolved STEM imaging reveal the difference in out-of-plane lattice parameters in the stacked thin film, which is further quantified on a larger scale using four-dimensional STEM (4D-STEM). In the layer deposited at a lower temperature, electron energy loss spectroscopy (EELS) mapping indicates drastic changes in the oxidation states and bonding environment for Co ions, and energy-dispersive X-ray spectroscopy (EDX) mapping detects more significant cation deficiency. Ab initio density functional theory (DFT) calculations validate that vacancies on the cation sublattice of J14 result in significant electronic and structural changes. The experimental and computational analyses indicate that low temperatures during film growth result in cation deficiency, an altered chemical environment, and reduced lattice parameters while maintaining a single phase. Our results demonstrate that the complex correlation of configurational entropy, kinetics, and thermodynamics can be utilized for accessing a range of metastable configurations in HEO materials without altering cation proportions, enabling further engineering of functional properties of HEO materials.

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

Long-term thermal aging of parylene conformal coating under high humidity and its effects on tin whisker mitigation

Usage of pure tin (Sn) or Sn-rich alloy in electronics industry is growing, which makes them more susceptible to the spontaneous growth of tin whiskers. The risk of having these whiskers can be dramatically mitigated by applying a conformal coating provided that it not only possesses excellent mechanical and adhesion properties but also maintains these properties throughout their service. Parylene C is commonly used as a conformal coating because of its favorable mechanical and physical properties, as well as superior conformal coverage. The purpose of this paper is to investigate the degradation of parylene C coating during the thermal aging in high humidity environment (85°C/85% relative humidity for up to 5000hrs) and its effect on the tin whisker mitigation capacity. It was observed that during aging at high temperature and high humidity (HTHH) environment, the oxidation occurs at early times, followed by bond scission, resulting in the loss of strength of the coating. Thinner parylene coating (12.5-μm-thick) had better coating adhesion on the silane-treated tin surface, so provided the better protection for tin whisker penetration than the thicker counterpart (25-μm-thick). After 2500hrs of aging, due to the degradation of the silane agent at the tin/parylene interface, the adhesion of the parylene coating was significantly weakened on the tin surface, which resulted in extensive corrosion of the tin solderpads. The loss of adhesion of the coating, along with the corrosion of the tin surface facilitated the tin whisker nucleation at the interface while the loss of mechanical strength and the brittleness made the coating easily penetrated by the growing whiskers. Tin whiskers with a smaller diameter were buckled and grew along the delaminated region while those with a larger diameter penetrated and continued to grow through the coating. Hence, the effectiveness of the parylene coatings on tin whisker mitigation is significantly reduced under long exposure to such high temperature and high humidity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Molecular Origins of Near-Infrared Luminescence in Molybdenum and Tungsten Oxyhalide Perovskites

Materials with near-infrared (near-IR) luminescence are desirable for applications in communications and sensing, as well as biomedical diagnostics and imaging. The most used inorganic near-IR emitters rely on precise doping of host crystal structures with select rare-earth or transition metal ions. Recently, another class of materials with intrinsic near-IR emission has been reported. The compositions of these materials were initially described as vacancy-ordered halide double perovskites Cs 2 MoCl 6 and Cs 2 WCl 6 , but further investigation by some of us on the compound reported as Cs2WCl6 revealed an oxyhalide instead, with a composition Cs 2 WO x Cl 6–x , where 1 < x < 2. Here we demonstrate that the Mo compounds similarly possess the composition Cs 2 MoO x Cl 6–x or Cs 2 MoO x Br 6–x where 1 < x < 2. Preparing the pure halide appears harder for Mo than for W, and we have not succeeded in doing so. The distinctly different composition requires the coordination environment and oxidation state for the Mo and W centers to be reconsidered from what was assumed for the pure halides. In this work, we examine the mechanism for near-IR emission in these materials given their true structures and compositions. We demonstrate that the luminescence is due to the specific d-orbital splitting caused by the presence of oxygen in the distorted [MOX 5 ] 2– octahedra (X is Cl or Br). The fine structure in the emission spectra at low temperatures has been resolved and is attributed to vibronic coupling to the Mo–O and W–O bond stretches. Understanding the true structure and composition of these interesting materials, besides explaining the near-IR luminescence, suggests how this desirable emission can be realized and manipulated.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evidence of Inverse Hall-Petch Behavior and Low Friction and Wear in High Entropy Alloys

We present evidence of inverse Hall-Petch behavior for a single-phase high entropy alloy (CoCrFeMnNi) in ultra-high vacuum and show that it is associated with low friction coefficients (~0.3). Grain size measurements by STEM validate a recently proposed dynamic amorphization model that accurately predicts grain size-dependent shear strength in the inverse Hall-Petch regime. Wear rates in the initially soft (coarse grained) material were shown to be remarkably low (~10 –6 mm 3 /N-m), the lowest for any HEA tested in an inert environment where oxidation and the formation of mixed metal-oxide films is mitigated. The combined high wear resistance and low friction are linked to the formation of an ultra-nanocrystalline near-surface layer. The dynamic amorphization model was also used to predict an average high angle grain boundary energy (0.87 J/m 2 ). This value was used to explain cavitation-induced nanoporosity found in the highly deformed surface layer, a phenomenon that has been linked to superplasticity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The transformation of lepidocrocite (γ-FeOOH) with Fe($\tiny{II}$) (aq) in slightly acidic media: intermediate pathways and biomimetic behavior

Lepidocrocite (LP) is commonly found in natural or anthropogenic environments and oxidized alloy steel waste storage containers. Despite its importance, the end products formed and its mineral transformation pathways, including intermediate steps and underlying mechanisms under Fe(II) (aq) catalysis still need to be clarified due to decades of dispersed research. Here, in this work, we investigated LP's catalytic transformation with 10 mM and 0.2 mM Fe(II) (aq) at their natural solution pH's via bulk (X-ray Diffraction/XRD, Raman and Attenuated Total Reflectance Fourier Transform Infrared/ATR-FTIR) and micro/nano-scale (semi in situ Transmission Electron Microscopy/TEM) analysis. In general, we observed that goethite (GT) and LP were the main end products. However, a series of two major distinct intermediate events that were initiated by a dissolution type of reaction along with an “induction period” (lack of dissolution) on LP occurred. Fascinatingly, two of the intermediate steps along its mineral transformation presented novel types of non-classical mechanisms of crystallization via some type of guided oriented particle attachment. Furthermore, one of these intermediate steps is biomimetic in appearance, similar to what is observed during bacterial particle attachment. However, it uses inorganic nano-wire antennas that have a sensory-like function as observed with bacterial fimbriae and/or flagellum through an electron transparent film (similar to a bio-film matrix). Finally, this work leads us to comprehend the evolution of some well documented crystal morphologies for GT commonly observed in natural and anthropogenic settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Interface effect of Fe and Fe 2 O 3 on the distributions of ion induced defects

The stability of structural materials in extreme nuclear reactor environments—with high temperature, high radiation, and corrosive media—directly affects the lifespan of the reactor. In such extreme environments, an oxide layer on the metal surface acts as a passive layer protecting the metal underneath from corrosion. To predict the irradiation effect on the metal layer in these metal/oxide bilayers, nondestructive depth-resolved positron annihilation lifetime spectroscopy (PALS) and complementary transmission electron microscopy (TEM) were used to investigate small-scale defects created by ion irradiation in an epitaxially grown (100) Fe film capped with a 50 nm Fe 2 O 3 oxide layer. In this study, the evolution of induced vacancies was monitored, from individual vacancy formation at low doses—10 –5 dpa—to larger vacancy cluster formation at increasing doses, showing the sensitivity of positron annihilation spectroscopy technique. Furthermore, PALS measurements reveal how the presence of a metal–oxide interface modifies the distribution of point defects induced by irradiation. TEM measurements show that irradiation induced dislocations at the interface is the mechanism behind the redistribution of point defects causing their accumulation close to the interface. Finally, this work demonstrates that the passive oxide layers formed during corrosion impact the distribution and accumulation of radiation induced defects in the metal underneath and emphasizes that the synergistic impact of radiation and corrosion will differ from their individual impacts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

In-Situ Powder-Directed Energy Process Control for Additively Manufactured Multi-Layer, Functionally Graded Components

Coatings and cladding can experience damage in harsh environments: Erosion Oxidation Delamination External mechanical damage Radiation induced damage Functionally Graded Materials (FGMs) were primarily designed to reduce thermal stress in thermal barrier coatings (TBCs), but can produce coatings which resist a variety of material damage (corrosion, surface damage, diffusion) Powder-fed DED with multiple independent feeders allows for AM FGMs, and provides robust control over process parameters to optimize microstructure and performance. FGMs have a great opportunity for applications in energy applications as a strategy to increase plant efficiency and lifetime.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1979

Corona-discharge air-purification system

Plasma reaction chamber removes trace contaminants from spacecraft, submarines, and other closed environments by oxidizing contaminants to produce carbon dioxide and water. Contaminants are alcohols, esters, hydrogen sulfide, and ammonia. Others are lubricant solvents such as Freons, aromatics, and Ketones. Contaminants are removed from chamber by scrubber.

Wydeven, T. J.↗
NASA NTRS1984

Laboratory infrared studies relevant to Io: A satellite to the planet Jupiter

To explain the unidentified spectral features of Io, as obtained by the Voyager infrared spectrometer experiment, the infrared absorption spectra of a number of stable sulfur and oxygen compounds was measured and compared to the Voyager data. Based on the reference absorption bands of Na2SO4 and possibly SO2, the infrared data on Io in the region 700 to 200 per cm appear to represent an emission spectrum. Given the strong evidence for an oxidized crustal environment and the presence of sodium in the Io torus, the absorption spectra of the tested materials support the probability of Na2SO4 occurrence on Io.

Khanna, R. K.↗
NASA NTRS1987

Circumstellar radio molecular lines

Radio molecular lines appear to be useful probes into the stellar environment. Silicon oxide masers provide information on the physical conditions in the immediate vicinity of the stellar photosphere. Valuable information on the physics operating in the envelope of IRC + 10216 was recently obtained by high sensitivity observations and detailed theoretical analyses. Infrared speckle interferometry in the molecular lines and in the continuum is helpful in the investigation of the inner region of the envelope. These techniques are discussed in terms of late-type star mass loss.

NGUYEN-QUANG-RIEU↗
NASA NTRS1989

Undercutting of defects in thin film protective coatings on polymer surfaces exposed to atomic oxygen

Protection for polymeric surfaces is needed to make them durable in the low Earth orbital environment, where oxidation by atomic oxygen is the predominant failure mechanism. Thin film coatings of oxides such as silicon dioxide are viable candidates to provide this protection, but concern has been voiced over the ability of these coatings to protect when defects are present in the coating due to surface anomalies occurring during the deposition process, handling, or micrometeoroid and debris bombardment in low Earth orbit. When a defected coating protecting a polymer substrate is exposed to atomic oxygen, the defect provides a pathway to the underlying polymer allowing oxidation and subsequent undercutting to occur. Defect undercutting was studied for sputter deposited coatings of silicon dioxide on polyimide Kapton. Preliminary results indicate that undercutting may be limited as long as the coating remains intact with the substrate. Therefore, coatings may not need to be defect free to give protection to the underlying surface.

Rutledge, Sharon K.↗
NASA NTRS1989

Stable carbon and sulfur isotopes as records of the early biosphere

The abundance ratios of the stable isotopes of light elements such as carbon and sulfur can differ between various naturally-occurring chemical compounds. If coexisting compounds have achieved mutual chemical and isotopic equilibrium, then the relative isotopic composition can record the conditions at which equilibrium was last maintained. If coexisting chemical compounds indeed formed simultaneously but had not achieved mutual equilibrium, then their relative isotopic compositions often reflect the conditions and mechanisms associated with the kinetically controlled reactions responsible for their production. In the context of Mars, the stable isotopic compositions of various minerals might record not only the earlier environmental conditions of the planet, but also whether or not the chemistry of life ever occurred there. Two major geochemical reservoirs occur in Earth's crust, both for carbon and sulfur. In rocks formed in low temperature sedimentary environments, the oxidized forms of these elements tend to be enriched in the isotope having the larger mass, relative to the reduced forms. In sediments where the organics and sulfides were formed by biological processes, these isotopic contrasts were caused by the processes of biological CO2 fixation and dissimilatory sulfate reduction. Such isotopic contrasts between oxidized and reduced forms of carbon and sulfur are permitted by thermodynamics at ambient temperatures. However, nonbiological chemical reactions associated with the production of organic matter and the reduction of organics and sulfides are extremely slow at ambient temperatures. Thus the synthesis of organics and sulfides under ambient conditions illustrates life's profound role as a chemical catalyst that has altered the chemistry of Earth's crust. Because the stable isotopes of carbon and sulfur can reflect their chemistry, they are useful probes of the Martian surface.

Desmarais, David J.↗
NASA NTRS1990

Volatile compounds in shergottite and nakhlite meteorites

Since discovery of apparent carbonate carbon in Nakhla, significant evidence has accumulated for occurrence of volatile compounds in shergotties and nakhlites. Results are presented from a study of volatile compounds in three shergottites, one nakhlite, and three eucrite control samples. Shergotties ALHA77005, EETA79001, and Shergotty, and the nakhlite Nakhla, all contain oxidized sulfur (sulfate) of preterrestrial origin; sulfur oxidation is most complete in EETA79001/Lith-C. Significant bulk carbonate was confirmed in Nakhla and trace carbonate was substantiated for EETA79001, all of which appears to be preterrestrial in origin. Chlorine covaries with oxidized sulfur, whereas carbonate and sulfate are inversely related. These volatile compounds were probably formed in a highly oxidizing, aqueous environment sometime in the late stage histories of the rocks that are now represented as meteorites. They are consistent with the hypothesis that shergottite and nakhlite meteorites originated on Mars and that Mars has supported aqueous geochemistry during its history.

Gooding, James L.↗
NASA NTRS1993

Development of a molecular beam technique to study early solar system silicon reactions

Silicon monoxide is one of the major gas phase silicon bearing components observed in astronomical environments. Silicon oxide serves as the major rock forming material for terrestrial and meteoritic bodies. It is known that several gas phase reactions produce mass independent isotopic fractionations which possess the same delta(O-17)/delta(O-18) ratio observed in Allende inclusions. The general symmetry dependence of the chemically produced mass independent isotopic fractionation process suggests that there are several plausible reactions which could occur in the early solar system which may lead to production of the observed meteoritic oxygen isotopic anomalies. An important component in exploring the role of such processes is the need to experimentally determine the isotopic fractionations for specific reactions of relevance to the early solar system. It has already been demonstrated that atomic oxygen reaction with CO, a major nebular oxygen bearing species, produces a large (approximately 90 percent), mass independent isotopic fractionation. The next hurdle regarding assessing the involvement of symmetry dependent isotopic fractionation processes in the pre-solar nebula is to determine isotopic fractionation factors associated with gas phase reactions of metallic oxides. In particular, a reaction such as O + SiO yields SiO2 is a plausible nebular reaction which could produce a delta(O-17) is approximately delta(O-18) fractionation based upon molecular symmetry considerations. While the isotopic fractionations during silicate evaporation and condensation have been determined, there are no isotopic studies of controlled, gas phase nucleation processes. In order to carefully control the reaction kinetics, a molecular beam apparatus has been constructed. This system produces a supersonic, collimated beam of SiO molecules which is reacted with a second beam of oxygen atoms. An important feature of molecular beams is that they operate at sufficiently low pressures and high temperatures in the jet that avalanche nucleation and clustering processes may be avoided.

Dong, Q. W.↗