High-vacuum, low-temperature bond for second-surface mirrors
Indium solder reliably bonds second-surface mirrors to radiant coolers in cryogenic environments.
Mckeown, D.↗
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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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Slow crack growth in glass in combined mode I and mode II loading
Slow crack growth in soda-lime glass under combined mode I and mode II loading was investigated in precracked disk specimens in which pure mode I, pure mode II, and various combinations of mode I and mode II were achieved by loading in diametral compression at selected angles with respect to symmetric radial cracks. It is shown that slow crack growth under these conditions can be described by a simple exponential relationship with elastic strain energy release rate as the effective crack-driving force parameter. It is possible to interpret this equation in terms of theoretical models that treat subcritical crack growth as a thermally activated bond-rupture process with an activation energy dependent on the environment, and the elastic energy release rate as the crack-driving force parameter.
Shetty, D. K.↗
Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics
Plasma-sprayed mullite (3Al2O3 central dot 2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon-based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface, Thus modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.
Lee, Kang N.↗
Key Durability Issues with Mullite-Based Environmental Barrier Coatings for Si-Based Ceramics
Plasma-sprayed mullite (3Al2O3.2SiO2) and mullite/yttria-stabilized-zirconia (YSZ) dual layer coatings have been developed to protect silicon -based ceramics from environmental attack. Mullite-based coating systems show excellent durability in air. However, in combustion environments, corrosive species such as molten salt or water vapor penetrate through cracks in the coating and attack the Si-based ceramics along the interface. Thus the modification of the coating system for enhanced crack-resistance is necessary for long-term durability in combustion environments. Other key durability issues include interfacial contamination and coating/substrate bonding. Interfacial contamination leads to enhanced oxidation and interfacial pore formation, while a weak coating/substrate bonding leads to rapid attack of the interface by corrosive species, both of which can cause a premature failure of the coating. Interfacial contamination can be minimized by limiting impurities in coating and substrate materials. The interface may be modified to improve the coating/substrate bond.
Lee, Kang N.↗
Plasma Chemical Conversion and Resource Generation Beyond Low-Earth Orbit
As humanity gears up for its return to the moon after more than half a century, collaborative efforts between NASA, Artemis Accords Partners, and private industry are underway to establish the necessary infrastructure and technologies for lunar habitation and eventual Mars exploration. However, the traditional ISS resupply and waste management model is impractical and economically infeasible for prolonged missions to the Moon and Mars. Advanced chemical conversion technologies are needed to generate vital consumable products from local planetary resources (ISRU) and recycled gasses and waste within semi-closed loop life-support systems. Low-temperature plasma reactors are emerging power-to-gas technologies with the potential to facilitate various chemical synthesis processes with hardware commonality and redundancy. In plasma-based systems, electrical power is used to ionize a feedstock gas, creating a highly reactive environment that leverages electron excitation chemistry to break stable molecular bonds and form value added products. Unlike thermal chemical processes, plasma reactors operate at non-equilibrium conditions, allowing for lower-temperature operation and instantaneous start-up, making them adaptable to intermittent power availability. Moreover, their scalability permits deployment in both portable astronaut systems and large-scale industrial setups for colonies. One promising application of plasmas is for CO 2 conversion. Carbon dioxide comprises 96% of the Martian atmosphere and is a byproduct of human respiration, which typically must be scrubbed and vented from space habitats. A plasma source integrated with membrane separation technology could generate a stream of oxygen for life support and rocket propellant. CO 2 splitting may also be beneficial as a precursor to manufacture carbon-based products and fuels in situ, like methane, methanol, and polyethylene. Plasma-assisted CO 2 conversion is a simpler case to study without the concern of selectivity and is the first step toward complex chemical synthesis. This work presents preliminary experimental case study from a plasma reactor for CO 2 conversion and casts a vision for the potential of plasma technologies in a sub-architecture for resource production to enable the next generation of human spaceflight activities.
Plasma↗
A hybrid electronically scanned pressure module for cryogenic environments
Pressure is one of the most important parameters measured when testing models in wind tunnels. For models tested in the cryogenic environment of the National Transonic Facility at NASA Langley Research Center, the technique of utilizing commercially available multichannel pressure modules inside the models is difficult due to the small internal volume of the models and the requirement of keeping the pressure transducer modules within an acceptable temperature range well above the -173 degrees C tunnel temperature. A prototype multichannel pressure transducer module has been designed and fabricated with stable, repeatable sensors and materials optimized for reliable performance in the cryogenic environment. The module has 16 single crystal silicon piezoresistive pressure sensors electrostatically bonded to a metalized Pyrex substrate for sensing the wind tunnel model pressures. An integral temperature sensor mounted on each silicon micromachined pressure sensor senses real-time temperature fluctuations to within 0.1 degrees C to correct for thermally induced non-random sensor drift. The data presented here are from a prototype sensor module tested in the 0.3 M cryogenic tunnel and thermal equilibrium conditions in an environmental chamber which approximates the thermal environment (-173 degrees C to +60 degrees C) of the National Transonic Facility.
Chapman, J. J.↗
Dynamic Evolution of Palladium Single Atoms on Anatase Titania Support Determines the Reverse Water–Gas Shift Activity
Research interest in single-atom catalysts (SACs) has been continuously rising. However, the lack of understanding of the dynamic behaviors of SACs during applications hinder catalyst development and mechanistic understanding. Herein, we report on the evolution of active sites over Pd/TiO 2 -anatase SAC (Pd 1 /TiO 2 ) in the reverse water-gas shift (rWGS) reaction. Combining kinetics, in-situ characterization, and theory, we show that at T ≥ 350 °C, the reduction of TiO 2 by H 2 alters the coordination environment of Pd, creating Pd sites with partially cleaved Pd-O interfacial bonds and a unique electronic structure that exhibit high intrinsic rWGS activity through the carboxyl pathway. The activation by H 2 is accompanied by the partial sintering of single Pd atoms (Pd 1 ) into disordered, flat, ~1 nm diameter clusters (Pd n ). The highly active Pd sites in the new coordination environment under H 2 are eliminated by oxidation, which, when performed at high temperature, also re-disperses Pd n and facilitates the reduction of TiO 2 . In contrast, Pd 1 sinters into crystalline, ~5 nm particles (Pd NP ) during CO treatment, deactivating Pd 1 /TiO 2 . During the rWGS reaction, the two Pd evolution pathways co-exist. The activation by H 2 dominates, leading to the increasing rate with time-on-stream, and steady-state Pd active sites similar with the ones formed under H 2 . Finally, this work demonstrates how the coordination environment and nuclearity of metal sites on a SAC evolve during catalysis and pre-treatments, and how their activity is modulated by these behaviors. These insights on SAC dynamics and structure-function relationship are valuable to mechanistic understanding and catalyst design.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An S=1 Iron(IV) Intermediate Revealed in a Non-Heme Iron Enzyme-Catalyzed Oxidative C—S Bond Formation
Ergothioneine (ESH) and ovothiol A (OSHA) are two natural thiol-histidine derivatives. ESH has been implicated as a longevity vitamin and OSHA inhibits the proliferation of hepatocarcinoma. The key biosynthetic step of ESH and OSHA in the aerobic pathways is the O 2 -dependent C—S bond formation catalyzed by non-heme iron enzymes (e.g., OvoA in ovothiol biosynthesis), but due to the lack of identification of key reactive intermediate the mechanism of this novel reaction is unresolved. In this study, we report the identification and characterization of a kinetically competent S=1 iron(IV) intermediate supported by a four-histidine ligand environment (three from the protein residues and one from the substrate) in enabling C—S bond formation in OvoA from Methyloversatilis thermotoleran, which represents the first experimentally observed intermediate spin iron(IV) species in non-heme iron enzymes. Results reported in this study thus set the stage to further dissect the mechanism of enzymatic oxidative C—S bond formation in the OSHA biosynthesis pathway. They also afford new opportunities to study the structure-function relationship of high-valent iron intermediates supported by a histidine rich ligand environment.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Evaluation of chromic acid anodized aluminum foil coated composite tubes for the Space Station truss structure
This paper describes the development and evaluation of chromic acid anodized (CAA) Al foil as a protective and thermal control coating for graphite/epoxy tubes designed for the Space Station truss structure. Special consideration is given to the development of solar-absorptance and thermal-emittance properties required of Al foil, the development of CAA parameters necessary to achieve these optical properties, and the atomic oxygen and UV testing of CAA Al foil. Results showed that 0.003-in CAA Al foil cocured or secondary bonded to graphite/epoxy tubes with thin epoxy film adhesive retains excellent bond strength and provides a superior protective and thermal control coating to the LEO environment. Processes were developed for CAA Al foils long enough to continuously wrap the 23-ft-long diagonal struts of the Space Station truss structure. Specifications are presented for the processes of chromic acid anodizing of Al foil and for the bonding of anodized Al foil to graphite/epoxy tubes.
Dursch, Harry W.↗
Effects of Noncovalent Interactions on High-Spin Fe(IV)–Oxido Complexes
High-valent nonheme Fe IV –oxido species are key intermediates in biological oxidation, and their properties are proposed to be influenced by the unique microenvironments present in protein active sites. Microenvironments are regulated by noncovalent interactions, such as hydrogen bonds (H-bonds) and electrostatic interactions; however, there is little quantitative information about how these interactions affect crucial properties of high valent metal–oxido complexes. To address this knowledge gap, we introduced a series of Fe IV –oxido complexes that have the same S = 2 spin ground state as those found in nature and then systematically probed the effects of noncovalent interactions on their electronic, structural, and vibrational properties. The key design feature that provides access to these complexes is the new tripodal ligand [poat] 3– , which contains phosphinic amido groups. An important structural aspect of [Fe IV poat(O)] - is the inclusion of an auxiliary site capable of binding a Lewis acid (LA II ); we used this unique feature to further modulate the electrostatic environment around the Fe–oxido unit. Experimentally, studies confirmed that H-bonds and LA II s can interact directly with the oxido ligand in Fe IV –oxido complexes, which weakens the Fe=O bond and has an impact on the electronic structure. Additionally, we found that relatively large vibrational changes in the Fe–oxido unit correlate with small structural changes that could be difficult to measure, especially within a protein active site. Our work demonstrates the important role of noncovalent interactions on the properties of metal complexes, and that these interactions need to be considered when developing effective oxidants.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Test Data of Flow Field of Shuttle SRM Nozzle Joint with Bond Defects, Using Unheated Air
The nozzle-to-case joint on the Shuttle SRM (as redesigned after the Challenger accident) features an adhesive sealant filling and bonding the joint, with a wiper O-ring to prevent the adhesive from reaching and disabling the closure O-ring. Flawless implementation of that joint design would ensure that hot, corrosive propellant combustion gases never reach the closure O-ring. However, understanding the flow field related to bonding defects is prudent. A comprehensive test program was conducted to quantify such flow fields and associated heating environments. A two-dimensional, full-scale model represented 65 inches of the nozzle joint, using unheated air as the test medium, in a blowdown mode. Geometry variations modeled RSRM assembly tolerances, and two types of bonding defects: pullaways and blowholes. A range of the magnitude of each type defect was tested. Also a range of operational parameters was tested, representative of the RSRM flow environment, including duplication of RSRM Mach and Reynolds numbers. Extensive instrumentation was provided to quantify pressures, heat rates, and velocities. The resulting data established that larger geometric defects cause larger pressure and larger heating, at the closure O-ring region. Velocity trends were not so straight-forward. Variations in assembly tolerances did not generally affect flow fields or heating. Operational parameters affected flow fields and heating as might be expected, increasing density or velocity increased heating. Complete details of this test effort are presented.
Hair, Leroy M.↗
Intermediate Temperature Stress Rupture of Woven SiC Fiber, BN Interphase, SiC Matrix Composites in Air
Tensile stress-rupture experiments were performed on woven Hi-Nicalon reinforced SiC matrix composites with BN interphases in air. Modal acoustic emission (AE) was used to monitor the damage accumulation in the composites during the tests and microstructural analysis was performed to determine the amount of matrix cracking that occurred for each sample. Fiber fractograph), was also performed for individual fiber failures at the specimen fracture surface to determine the strengths at which fibers failed. The rupture strengths were significantly worse than what would have been expected front the inherent degradation of the fibers themselves when subjected to similar rupture conditions. At higher applied stresses the rate of rupture "?as larger than at lower applied stresses. It was observed that the change in rupture rate corresponded to the onset of through-thickness cracking in the composites themselves. The primary cause of the sen,ere degradation was the ease with which fibers would bond to one another at their closest separation distances, less than 100 nanometers, when exposed to the environment. The near fiber-to-fiber contact in the woven tows enabled premature fiber failure over large areas of matrix cracks due to the stress-concentrations created b), fibers bonded to one another after one or a few fibers fail. i.e. the loss of global load sharing. An@, improvement in fiber-to-fiber separation of this composite system should result in improved stress- rupture properties. A model was den,eloped in order to predict the rupture life-time for these composites based on the probabilistic nature of indin,idual fiber failure at temperature. the matrix cracking state during the rupture test, and the rate of oxidation into a matrix crack. Also incorporated into the model were estimates of the stress-concentration that would occur between the outer rim of fibers in a load-bearing bundle and the unbridged region of a matrix crack after Xia et al. For the lower stresses, this source of stress-concentration was the likely cause for initial fiber failure that would trigger catastrophic failure of the composite.
Morscher, Gregory N.↗
Avoiding CO 2 Improves Thermal Stability at the Interface of Li 7 La 3 Zr 2 O 12 Electrolyte with Layered Oxide Cathodes
Abstract Solid‐state batteries promise higher energy densities and better safety than Li‐ion batteries with liquid electrolytes. However, the interface between solid electrolyte and cathode is unstable at the elevated temperatures that are needed while sintering to achieve good bonding between ceramic components. Here, the hypothesis is that, the gas environment, especially the presence of CO 2, is critical in determining the stability of the solid electrolyte–cathode interface. The effect of gas species on the interface is systematically probed, by a using Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte with a thin film LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode as a model system to enable interface sensitivity. Detrimental phases formed at the interface and their onset conditions are identified by X‐ray absorption spectroscopy, X‐ray diffraction, and Gibbs free energy analysis. As a result, removing CO 2 and minimizing H 2 O(g) during sintering is necessary to obtain good contact at the LLZO|cathode interface without forming secondary phases. Sintering in O 2 is ideal, yielding excellent chemical stability and low interfacial resistance. Secondary phases also do not form in N 2, but oxygen loss occurs at elevated temperatures. The interfacial resistance obtained upon sintering in pure O 2 is comparable to the lowest values at LLZO interfaces with protective coatings, but here without the need for interface coatings.
25 ENERGY STORAGE↗
Atomically Dispersed Dual‐Metal Site Catalysts for Enhanced CO 2 Reduction: Mechanistic Insight into Active Site Structures
Abstract Carbon‐supported nitrogen‐coordinated single‐metal site catalysts (i.e., M−N−C, M: Fe, Co, or Ni) are active for the electrochemical CO 2 reduction reaction (CO 2 RR) to CO. Further improving their intrinsic activity and selectivity by tuning their N−M bond structures and coordination is limited. Herein, we expand the coordination environments of M−N−C catalysts by designing dual‐metal active sites. The Ni‐Fe catalyst exhibited the most efficient CO2RR activity and promising stability compared to other combinations. Advanced structural characterization and theoretical prediction suggest that the most active N‐coordinated dual‐metal site configurations are 2N‐bridged (Fe‐Ni)N 6 , in which FeN 4 and NiN 4 moieties are shared with two N atoms. Two metals (i.e., Fe and Ni) in the dual‐metal site likely generate a synergy to enable more optimal *COOH adsorption and *CO desorption than single‐metal sites (FeN 4 or NiN 4 ) with improved intrinsic catalytic activity and selectivity.
Li, Yi↗
Physical structure of constitutional isomers influences antiproliferation activity of thiosemicarbazone-alkylthiocarbamate copper complexes
A series of hybrid thiosemicarbazone-alkylthiocarbamate copper complexes with similar electronic environments but distinct physical structures have been prepared, characterized, and evaluated for antiproliferation activity. The complexes include the constitutional isomers (1-phenylpropane-1-imine-(O-ethylthiocarbamato)-2-one-(N-methylthiosemicarbazonato))copper(II) (CuL 1 ) and (1-phenylpropane-1-one-(N-methylthiosemicarbazonato)-2-imine-(O-ethylthiocarbamato))copper(II) (CuL 2 ) along with (1-propane-1-imine-(O-ethylthiocarbamato)-2-one-(N-methylthiosemicarbazonato))copper(II) (CuL 3 ). Complexes CuL 1 and CuL 2 differ in the positions of the pendent thiosemicarbazone (TSC) and alkylthiocarbamate (ATC) moieties on the 1-phenylpropane backbone. Complex CuL 3 employs a propane backbone with the TSC in the 2-position as in CuL 1 . The isomer pair CuL 1 and CuL 2 have equivalent electronic environments with indistinguishable Cu II/I potentials (E 1/2 = -0.86 V vs. ferrocenium/ferrocene) and electron paramagnetic resonance (EPR) spectra (g ∥ = 2.26, g ⊥ = 2.08). The electronic structure of CuL 3 has a similar E 1/2 of -0.84 V and identical EPR parameters to CuL 1, 2 . Single crystal X-ray diffraction studies confirm a consistent donor environment with no substantial variation in the Cusingle bondN or Cusingle bondS bond distances and angles between the complexes. The antiproliferation activities of the CuL 1–3 were evaluated against the lung adenocarcinoma cell line (A549) and nonmalignant lung fibroblast cell line (IMR-90) using the MTT assay. CuL 1 had the highest A549 activity ( A549 EC 50 = 0.065 μM) and selectivity ( IMR-90 EC 50 / A549 EC 50 = 20). The constitutional isomer CuL 2 displayed decreased A549 activity (0.18 μM) and selectivity (10.6). The complex CuL 3 displayed activity (0.009 μM) similar to CuL 1 but with a lack of selectivity (1.0). Cellular copper loading determined by ICP-MS was consistent with the activity and selectivity trends. The complexes CuL 1–3 did not induce reactive oxygen species (ROS) generation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy
Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.
25 ENERGY STORAGE↗
Dynamics of inverse metal oxides on metal catalysts using spectro-kinetics: reversible Brønsted acid site formation and irreversible reduction
Brønsted acid sites (BASs) in inverse catalysts are vital for the selective hydrogenolysis of polyols, specifically cleaving secondary C–O bonds. These BASs form dynamically in situ in an H 2 environment. While H 2 enables rapid BAS generation on short timescales, it reduces the catalyst at prolonged exposures. The active center for BAS generation, the kinetics of BAS formation, its reverse decomposition, and the irreversible oxide reduction have lacked direct experimental evidence. Here, aided by advanced spectro-kinetic studies, we identify trimeric W 3 O x sites on Pt as the active centers for BAS generation, whereas isolated WO x species on SiO 2 act merely as spectator species, demonstrated using an inverse WO x /Pt catalyst as a representative system. A detailed kinetic profile capturing the dynamics of W 3 O x sites on Pt is also established. The rate constant for BAS formation is two orders of magnitude higher than for its decomposition, which is one order of magnitude faster than the irreversible site reduction. Co-fed H 2 O suppresses the site reduction by ∼50%. Furthermore, the H 2 partial pressure plays an important role. While lower gas-phase H 2 partial pressure does not influence the reversible BAS formation, it can significantly (∼3×) suppress catalyst reduction. Finally, these findings offer critical insights into optimizing reaction conditions through periodic H 2 pulsing, enhancing catalyst stability and performance in hydrogenolysis reactions.
Sourav, Sagar [Indian Inst. of Technology (IIT), M↗
Ground/bonding for Large Space System Technology (LSST)
The influence of the environment and extravehicular activity remote assembly operations on the grounding and bonding of metallic and nonmetallic structures is discussed. Grounding and bonding philosophy is outlined for the electrical systems and electronic compartments which contain high voltage, high power electrical and electronic equipment. The influence of plasma and particulate on the system was analyzed and the effects of static buildup on the spacecraft electrical system discussed. Conceptual grounding bonding designs are assessed for capability to withstand high current arcs to ground from a high voltage conductor and electromagnetic interference. Also shown were the extravehicular activities required of the space station and or supply spacecraft crew members to join and inspect the ground system using manual on remote assembly construction.
Dunbar, W. G.↗