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365 records · Page 2

Spacecraft thermal control coatings: Comparison between flight results obtained on LDEF and MIR

The COMES experiment was installed outside of the MIR space station during an extravehicular activity. The experiment was exposed to vacuum, atomic oxygen, and ultraviolet radiation (UV) for 1.1 years. Due to a lack of knowledge about the spacecrafts actual attitude, there is a large uncertainty in the atomic oxygen fluence and the UV dose that was experienced by COMES. Additionally, contaminants of many different origins were observed on the COMES samples.

Jean-Claude Guillaumon

Monte Carlo modeling of atomic oxygen attack of polymers with protective coatings on LDEF

Characterization of the behavior of atomic oxygen interaction with materials on the Long Duration Exposure Facility (LDEF) will assist in understanding the mechanisms involved, and will lead to improved reliability in predicting in-space durability of materials based on ground laboratory testing. A computational simulation of atomic oxygen interaction with protected polymers was developed using Monte Carlo techniques. Through the use of assumed mechanistic behavior of atomic oxygen and results of both ground laboratory and LDEF data, a predictive Monte Carlo model was developed which simulates the oxidation processes that occur on polymers with applied protective coatings that have defects. The use of high atomic oxygen fluence-directed ram LDEF results has enabled mechanistic implications to be made by adjusting Monte Carlo modeling assumptions to match observed results based on scanning electron microscopy. Modeling assumptions, implications, and predictions are presented, along with comparison of observed ground laboratory and LDEF results.

Bruce A. Banks

Strategic Melamine Coating on Lithium Metal for Li 3 N-Rich Solid Electrolyte Interphase and Improved Battery Cycling Stability

The practical applications of lithium (Li) metal batteries (LMBs) are limited by challenges such as dendrite formation and unstable solid electrolyte interphase (SEI), especially at higher C-rates. Here, this study introduces melamine-coated Li metal anodes (LMAs), forming a Li 3 N-rich SEI layer that improves ionic conductivity and mechanical stability. The optimized melamine-coated LMA demonstrated uniform coverage resulting in denser Li deposition, nearly doubled cycle life (~148 cycles at 0.5 C, 1C = 4.1 mA cm -2 ), compared to Bare-Li. These findings emphasize that coating materials-induced beneficial SEI components could lead to improvement of LMB performance.

Batteries

Scalable slot-die coating of phyllosilicate membranes for selective ion separations

Abstract Two-dimensional (2D) materials have recently drawn attention as candidate materials for molecular-scale membrane separations due to their tunable nanoscale interlayer properties. Phyllosilicates, a broad class of naturally abundant 2D clay minerals, offer significant advantages over synthetic 2D materials, including low cost, stability, and environmental compatibility. While these properties make phyllosilicates attractive for industrial-scale nanofiltration applications, phyllosilicate-based membranes have, to date, only been fabricated at the lab scale via vacuum filtration. Scalable fabrication methods are essential to advance the technical maturity of phyllosilicate membranes and bring these promising materials closer to large-scale adoption. Herein, we have successfully scaled up phyllosilicate (vermiculite) membrane fabrication via slot-die coating and roll-to-roll coating of an ethylenediamine–vermiculite (EDAVM) mixture onto nylon. The coated membranes are 1–2 μm $ \unicode{x03BC} \mathrm{m} $ mu m in thickness and exhibit similar structure and performance to vacuum-filtered EDAVM membranes. The membranes also show selectivity for monovalent ions over multivalent ions in binary salt mixtures. This work represents a major step toward scaling up phyllosilicate membranes for industrial ion separation applications such as resource recovery from water.

Booth, Austin [Princeton University]

Eliminating chemo-mechanical degradation of lithium solid-state battery cathodes during >4.5 V cycling using amorphous Nb2O5 coatings

Abstract Lithium solid-state batteries offer improved safety and energy density. However, the limited stability of solid electrolytes (SEs), as well as irreversible structural and chemical changes in the cathode active material, can result in inferior electrochemical performance, particularly during high-voltage cycling (>4.3 V vs Li/Li + ). Therefore, new materials and strategies are needed to stabilize the cathode/SE interface and preserve the cathode material structure during high-voltage cycling. Here, we introduce a thin (~5 nm) conformal coating of amorphous Nb 2 O 5 on single-crystal LiNi 0.5 Mn 0.3 Co 0.2 O 2 cathode particles using rotary-bed atomic layer deposition (ALD). Full cells with Li 4 Ti 5 O 12 anodes and Nb 2 O 5 -coated cathodes demonstrate a higher initial Coulombic efficiency of 91.6% ± 0.5% compared to 82.2% ± 0.3% for the uncoated samples, along with improved rate capability (10x higher accessible capacity at 2C rate) and remarkable capacity retention during extended cycling (99.4% after 500 cycles at 4.7 V vs Li/Li + ). These improvements are associated with reduced cell polarization and interfacial impedance for the coated samples. Post-cycling electron microscopy analysis reveals that the Nb 2 O 5 coating remains intact and prevents the formation of spinel and rock-salt phases, which eliminates intra-particle cracking of the single-crystal cathode material. These findings demonstrate a potential pathway towards stable and high-performance solid-state batteries during high-voltage operation.

Science & Technology - Other Topics

The Effects of Lunar Dust on EVA Systems During the Apollo Missions

Mission documents from the six Apollo missions that landed on the lunar surface have been studied in order to catalog the effects of lunar dust on Extra-Vehicular Activity (EVA) systems, primarily the Apollo surface space suit. It was found that the effects could be sorted into nine categories: vision obscuration, false instrument readings, dust coating and contamination, loss of traction, clogging of mechanisms, abrasion, thermal control problems, seal failures, and inhalation and irritation. Although simple dust mitigation measures were sufficient to mitigate some of the problems (i.e., loss of traction) it was found that these measures were ineffective to mitigate many of the more serious problems (i.e., clogging, abrasion, diminished heat rejection). The severity of the dust problems were consistently underestimated by ground tests, indicating a need to develop better simulation facilities and procedures.

James R Gaier

The Effects of Lunar Dust on EVA Systems During the Apollo Missions

Mission documents from the six Apollo missions that landed on the lunar surface have been studied in order to catalog the effects of lunar dust on Extra-Vehicular Activity (EVA) systems, primarily the Apollo surface space suit. It was found that the effects could be sorted into nine categories: vision obscuration, false instrument readings, dust coating and contamination, loss of traction, clogging of mechanisms, abrasion, thermal control problems, seal failures, and inhalation and irritation. Although simple dust mitigation measures were sufficient to mitigate some of the problems (i.e., loss of traction) it was found that these measures were ineffective to mitigate many of the more serious problems (i.e., clogging, abrasion, diminished heat rejection). The severity of the dust problems were consistently underestimated by ground tests, indicating a need to develop better simulation facilities and procedures.

James R Gaier

Boron-Based Neutron Scintillator Screen Characterization with X-Rays and Neutrons

Recent work on boron-based neutron scintillator screens suggests these screens can offer superior performance when compared to commonly used screens. Borated neutron scintillator screens perform well in terms of light output (5-6 times greater than a standard Gadox screen) and detection effi-ciency (larger than standard LiF+ZnS screens). However, previously manu-factured boron-based screens have exhibited non-uniform surface coating and a poor mixture between phosphor and converter particles. The objective of this work was to evaluate newly fabricated scintillator screens to deter-mine if enhanced fabrication methods produced a more homogeneous distribution between neutron converter and scintillation phosphor particles. Uniformity of scintillator material deposition was also inspected. This new iteration of screens appeared more uniform than previous generations with the new coating method improving surface chemistry and scintillator material homogeneity. Additionally, a new methodology for screen characterization, involving the correlation of a neutron image taken with a borated scintillator screen to X-ray computed tomography of that same screen, was demonstrated to elucidate a relationship between scintillator screen thickness and relative light output of the screen under neutron exposure. This method suggested that the ideal thickness of scintillator material was ~150 µm to maximize light output of the screen.

36 - MATERIALS SCIENCE

Efficient Leaching of Metal Ions from Spent Li-Ion Battery Combined Electrode Coatings Using Hydroxy Acid Mixtures and Regeneration of Lithium Nickel Manganese Cobalt Oxide

Extensive use of Li-ion batteries in electric vehicles, electronics, and other energy storage applications has resulted in a need to recycle valuable metals Li, Mn, Ni, and Co in these devices. In this work, an aqueous mixture of glycolic and lactic acid is shown as an excellent leaching agent to recover these critical metals from spent Li-ion laptop batteries combined with cathode and anode coatings without adding hydrogen peroxide or other reducing agents. An aqueous acid mixture of 0.15 M in glycolic and 0.35 M in lactic acid showed the highest leaching efficiencies of 100, 100, 100, and 89% for Li, Ni, Mn, and Co, respectively, in an experiment at 120 °C for 6 h. Subsequently, the chelate solution was evaporated to give a mixed metal-hydroxy acid chelate gel. Pyrolysis of the dried chelate gel at 800 °C for 15 h could be used to burn off hydroxy acids, regenerating lithium nickel manganese cobalt oxide, and the novel method presented to avoid the precipitation of metals as hydroxide or carbonates. The Li, Ni, Mn, and Co ratio of regenerated lithium nickel manganese cobalt oxide is comparable to this metal ratio in pyrolyzed electrode coating and showed similar powder X-ray diffractograms, suggesting the suitability of α-hydroxy carboxylic acid mixtures as leaching agents and ligands in regeneration of mixed metal oxide via pyrolysis of the dried chelate gel.

Electrochemistry

Stoichiometric effects on grain growth in zirconium carbide coatings for high-temperature nuclear fuel

Interest in coated particle fuel for space nuclear propulsion (SNP) has expanded in recent years due to successful demonstrations of the resiliency of the coatings to extreme environments. For SNP applications, the coating layer for the particle design needs to be able to withstand exposure to high temperature hydrogen during operating conditions. ZrC has been proposed as a protective layer, however, it is important to understand the high temperature behavior to ensure adequate protection to this fuel. In this study, surrogate ZrC coated particles were heat treated at 1900 °C up to 300 min, to examine how the microstructure evolves when exposed to high temperature. Scanning electron microscopy and electron backscatter diffraction (EBSD) were conducted to determine grain size and grain boundary character and orientation to determine the degree of change in the ZrC layer post heat treatment. Raman spectroscopy provided insight to understand how the as-fabricated stoichiometry of each sample contributed to the differences in grain growth behavior. Despite the as-fabricated samples showing a similar initial grain size and grain boundary character, the samples with a higher amount of excess carbon exhibited smaller grain areas and slower growth rates when exposed to 1900 °C. In conclusion, this investigation details the as-fabricated microstructure of the ZrC layer, specifically grain size, evolved under high temperature as this can impact the performance of the fuel under operating conditions.

EBSD

Thermodynamics of Tritium Trapping by Point Defects at Interfacial Cr-based Phases of the Al Coating

Density functional theory (DFT) simulations have been carried out to evaluate the potential for tritium trapping by metal vacancies in four phases Cr-containing phases (i.e., Cr3Si, Al0.3Cr0.7, Al8Cr5-HT, and Al8Cr5) identified near the interface between the Al coating and 316 stainless steel (316 SS) cladding. In addition, an ab initio thermodynamics approach has been employed to predict the temperature and T2-partial pressure dependence on the thermodynamics of singly tritiated defects. Key results in this work suggest that metal vacancies in the four phases have the potential to favorably trap tritium species, especially Si vacancies in Cr3Si phase. This overall thermodynamic trend can be correlated to the energy cost of having an interstitial tritium in the lattice, which has been calculated to range from 0.17 eV in Al8Cr5-HT to 0.89 eV in Cr3Si. A comparison of the results from this study with previous theoretical works investigating tritium behavior in other Fe-Al phases identified in the aluminide coating, suggests that metal vacancies are generally able to trap tritium in various Fe-Al aluminide phases. Especially, it was found that Si and Al vacancies would be the most efficient to trap for tritium, followed by Cr vacancies, then Fe and Ni vacancies. In the four Cr-based material phases investigated in this work, it is interesting to note that, in the absences of Fe or Ni species, strong interactions between tritium and the metal vacancies are always occurring by the formation of preferential Cr—T bonds (i.e., no Si—T or Al—T bonds were formed).

Sassi, Michel J.

Investigating Dual Electrospinning as a Means of Enhancing Passive Thermal Control Coatings for Cryogenic Propellant Storage in Extraterrestrial Environments

Passive thermal control is necessary as space exploration becomes increasingly widespread. Materials with superior optical properties (high solar reflectance and infrared emittance) are critical for passive thermal control because they can reject most of the incident solar radiation and promote thermal emission from cryogenic propellant storage tanks, enabling the extraterrestrial storage of cryogens. We have demonstrated in previous studies that electrospun nanofibers exhibit exceptional optical properties, offering significant benefits for passive radiative cooling in space. Particularly, electrospun polyvinylidene fluoride-co-hexafluoropropylene PVDF-HFP nanofibers demonstrate exceptionally high solar reflectance (>99%) and strong thermal emittance (measured at ~300 K). However, they exhibit nanostructural changes in the presence of atomic oxygen, which is prevalent in Low Earth Orbit. This study focuses on creating a unique blend of polymeric (PVDF-HFP) and ceramic-based (silica) nanofibers by leveraging the chemical stability and atomic oxygen resistance of silica, using the dual electrospinning manufacturing method. This approach aims to preserve the structural properties of the polymeric counterpart without compromising its optical performance, thereby providing an innovative method for manufacturing environmentally resilient passive thermal control nanofibers with desirable optical and thermal control functionalities for extraterrestrial storage of cryogenic propellants.

Chieloka Ibekwe

Assessing the Adhesion of Nanofibrous PVDF-HFP as Passive Thermal Control Coatings for the Extraterrestrial Storage of Cryogenic Propellants

Cryogenic propellant passive thermal management techniques in space are essential complements to active thermal management methods, helping reduce absolute dependence on the latter. Particularly, materials with superior optical properties (high solar reflectance and infrared emittance) would be beneficial for passive thermal control to reject most of the incident solar radiation and enhance thermal emission from the storage tank, leading to self-cooling. We developed a nanofibrous, porous passive thermal control material by electrospinning polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) co-polymer onto an aluminum foil substrate. The material exhibits a very high solar reflectance (>99%) and infrared emittance (~86%) when characterized in the ultraviolet-visible-near infrared and mid-infrared wavelengths. This study focuses on the adhesion of the nanofibrous PVDF-HFP to the substrate. We incorporated in-lab fabricated and commercial adhesives, under normal room conditions, between the nanofibers and the aluminum foil substrate to improve their adhesion. Some samples were also exposed to space-like conditions – vacuum and thermal cycling, to investigate their effects on the strengths of adhesives. Subsequently, adhesion peel tests were conducted on all the samples to assess the peel strengths of the bonds. Peel test strengths after space environment conditioning of the adhesives were generally higher than those observed in the pristine, unaged samples. The results are discussed in this study.

Chieloka Ibekwe

Advancements in nanocomposites for enhancing the performance of rechargeable lithium-ion batteries

The benefits of nanotechnology have been realized in almost every component of lithium-ion batteries. From electrodes to electrolytes, the incorporation of nanoparticles as dopants and coatings has shown marked improvements in cell cycle life, efficiency, mechanical and thermal stabilities, and lithium-ion transport. The improvements realized depends on several factors, from processing methods, nanoparticle type, structure, and concentration, to the material into which the nanoparticulate will be incorporated. Regardless of these many factors, nanotechnology has vastly improved the performance of secondary lithium-ion batteries. Here we will highlight some of the works that demonstrate these improvements and the quantitative benefits of nanotechnology.

25 ENERGY STORAGE

Symposium on Thermal Radiation of Solids

The Symposium was intended to provide for presentation and discussion of significant developments in the theory of thermal radiation of solids and in our understanding of the important effects of surfaces and interfaces and of surface imperfections on this radiation, of the effects of the space environment on radiation properties, and of the application of this information to the thermal designer's problems. Presentation of data as such-for example, absorptances and emittances of various types of coatings-was not considered a primary purpose of the Symposium; nevertheless, as the reader will observe, an appreciable amount of significant data of this type is contained in some of the papers. Developments in measurement techniques were also not considered basic to the main theme, especially since it was the theme of the preceding Symposium. However, because the subject remains of continuing concern, one session was devoted to it. These Proceedings contain all the papers presented orally at the Symposium together with the discussions that followed them, and, in addition, nine papers that were accepted for publication only. Each paper was reviewed by the session chairman and by the editor, and any apparent technical discrepancies were called to the attention of the author for clarification. As a further aid to the reader, the editor has tried to achieve some degree of uniformity in organization and format of the papers—at least to the extent permitted by the subject matter, and he has also striven for clarity and readability of the text. In this task he has had not only the cooperation of the authors but also extensive help from the Langley Technical Editing Section, the Langley Library (where most of the cited references were checked), and the NASA Headquarters Technical Publications Branch.

Solids

A General Solution Route to Nanoporous Metal Oxide Films

Metal oxide semiconductors are of interest as efficient, stable, and low-cost photoanode materials for photoelectrochemical water splitting, but their characteristically poor charge transport properties remain a fundamental challenge to practical use. Nanoporous metal oxide films that feature open bicontinuous networks of nanocrystals and nanopores can overcome such inefficient charge transport to enable high-performance photoanodes. Here, this paper describes a general method to make high-quality nanoporous films of metal oxides by spin coating and calcining molecular inks that contain a porosity-generating block copolymer. Phase-pure nanoporous films of BiFeO 3 , FeWO 4 , WO 3 , Fe 2 O 3 , and TiO 2 serve to demonstrate the versatility of the approach. It is demonstrated that the crystallite size, film porosity, and film thickness can be independently tuned by adjusting the ink composition and film processing conditions. The method is extended to fabricate core–shell nanoporous films consisting of a nanoporous film coated in a thin shell of a second metal oxide, using WO 3 –BiVO 4 and BiFeO 3 –BiVO 4 as examples. Given its simplicity and flexibility, this solution-phase route should prove useful for making nanoporous films of many different materials for a variety of applications, including energy conversion and storage, catalysis, and chemical sensing.

coating materials

Self‐Propelling Macroscale Sheets Powered by Enzyme Pumps

Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano‐ and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self‐propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter‐scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Degradation of optical components in a space environment

The objective of the Phillips Laboratory (PL) Long Duration Exposure Facility (LDEF) experiment is to determine the adverse effects of the natural space environment on laser optical component and coating materials. The LDEF experiment provides a unique opportunity for the study of optical material response to an extended low earth orbit space exposure. The PL samples consist of 10 sets of the six materials each. The materials are uncoated fused silica, magnesium fluoride coated fused silica, uncoated molybdenum, molybdenum coated with chromium, silver and thorium fluoride, diamond turned copper, and diamond turned nickel plated copper. Performance degradation will be correlated to establish trends between sample location, duration of exposure, atomic oxygen exposure and other space environmental conditions. This paper discusses the results of the tests thus far performed on the LDEF samples and the plans for the future.

Linda L. Dehainaut