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At least 127 records · Page 7

Single-Atom Nickel Dispersed on Mo 2 TiC 2 T x MXene for Upcycling of Polyolefins via Catalytic Hydropyrolysis for Fuels and Lubricants

Plastic waste has been a major social and environmental problem. Chemical upcycling of plastic waste into transportation fuels or lubricant oil has emerged as an attractive and promising approach to convert plastic waste into valuable products. However, conventional catalyst systems often require high-pressure hydrogen, prolonged residence time, and the use of noble metal catalysts. Here, we present zero-valent nickel single atoms on Mo-based MXenes (Ni/Mo 2 TiC 2 T x ) for effective hydrogenation of polyolefins. In situ spectroscopic and microscopic characterizations demonstrate the formation of Ni–Mo and Ni–C bonds at a low Ni loading, resulting in the formation of dispersed intercalated Ni atoms. The catalysts were then employed to convert polyethylene into fuels and lubricant molecules under atmospheric hydrogen pressure, short vapor residence time (τ < 1 s), and mild reaction temperature (300 °C). We further demonstrated the possibility of tuning the Ni structure by changing the Ni loading, attributed to the strong metal–support interactions (MSIs) with the Mo 2 TiC 2 T x support. Under optimized conditions, 22.5 C% gasoline, 12.0 C% diesel, 19.2 C% jet fuel (JP-8), and 37.4 C% lubricant were produced over 0.5% Ni/Mo 2 TiC 2 T x . This work highlights the potential of utilizing MSIs of Mo 2 TiC 2 T x MXenes to synthesize single-atom catalysts (SACs) for upcycling plastic waste into higher-value products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Complete Phase Transformation of Ir Nanowire Network into Defect-Rich Oxide Catalyst for High-Performance PEM Water Electrolysis

Iridium-based catalysts remain the most reliable option for the oxygen evolution reaction (OER) in proton exchange membrane water electrolyzers (PEMWEs). However, their high cost and limited performance represent critical barriers to the commercialization of this green hydrogen production technology. Herein, we report the creation of a metallic Ir nanowire network (IrNWN), which exhibits superior OER performance through its in-situ transition into an oxide structure with high intrinsic activity. At a low loading of 0.25 mgIr/cm2 in PEMWEs, IrNWN achieved a current density of 3.13 A/cm2 at a cell voltage of 1.8 V, outperforming the commercial Ir-based catalyst and surpassing the Department of Energy (DOE) 2026 technical target. Moreover, the high activity of IrNWN was maintained for 900 hours in a durability test at 2 A/cm2, showing a low degradation rate of 0.042 mV/hour. Structural analysis of the electrochemically oxidized IrNWN revealed the presence of mixed Ir oxidation states and a high density of surface terminal oxygen groups (μ1-O), which contributed to a reduced energy barrier for the rate-determining O-O coupling step.

oxygen evolution reaction↗

Fundamental Understanding of “Fresh” Lithium Nucleation and Growth in Sulfide-Based Anode-Free Solid-State Batteries: Effects of Substrate, Current Density, and Li + Supply

Understanding the electrochemical extraction and deposition of lithium (Li) from cathode is crucial for advancing anode-free solid-state batteries (AFSSBs). Herein, cryo-transmission electron microscopy (cryo-TEM) and electrochemical studies are employed to investigate how current collector surface properties, current densities, and cathode loadings influence the morphology of fresh electrochemically deposited Li and the electrochemical performance in sulfide-based AFSSBs. Cryo-TEM reveals that Cu current collectors induce irregular, dendritic Li deposits due to their lithiophobic nature and reactivity with Li 5.4 PS 4.4 Cl 1.6 (LPSC), while Ni and Au facilitate more uniform, planar-like Li growth. The morphology of the deposited Li also depends on current density: higher rates produce smaller, porous particles versus larger, denser deposits at lower rates. Importantly, for the first time, we discovered that low cathode loadings lead to poor cycling stability due to insufficient Li + supply for complete anode coverage, contrary to conventional solid-state batteries with preloaded Li metal anodes. This finding establishes a design principle where adequate cathode Li + reservoirs are essential for anode interface stability in AFSSBs. Overall, this work elucidates the interplayed effect of current collectors, current densities, and cathode loadings on Li morphology and cycle stability, offering fundamental insights into cathode-derived Li behavior and practical guidelines for optimizing AFSSBs performance through nucleation control and interface engineering.

25 ENERGY STORAGE↗

Testing Seam Concepts for Advanced Multilayer Insulation

Multilayer insulation (MLI) is considered the state of the art insulation for cryogenic propellant tanks in the space environment. MLI traditionally consists of multiple layers of metalized films separated by low conductivity spacers. In order to better understand some of the details within MLI design and construction, GRC has been investigating the heat loads caused by multiple types of seams. To date testing has been completed with 20 layer and 50 layer blankets. Although a truly seamless blanket is not practical, a blanket lay-up where each individual layer was overlapped and tapped together was used as a baseline for the other seams tests. Other seams concepts tested included: an overlap where the complete blanket was overlapped on top of itself; a butt joint were the blankets were just trimmed and butted up against each other, and a staggered butt joint where the seam in the out layers is offset from the seam in the inner layers. Measured performance is based on a preliminary analysis of rod calibration tests conducted prior to the start of seams testing. Baseline performance for the 50 layer blanket showed a measured heat load of 0.46 Watts with a degradation to about 0.47 Watts in the seamed blankets. Baseline performance for the 20 layer blanket showed a measured heat load of 0.57 Watts. Heat loads for the seamed tests are still begin analyzed. So far analysis work has suggested the need for corrections due to heat loads from both the heater leads and the instrumentation wires. A careful re-examination of the calibration test results with these factors accounted for is also underway. This presentation will discuss the theory of seams in MLI, our test results to date, and the uncertainties in our measurements.

multilayer insulation↗

Additive Manufacturing at NASA

Additive Manufacturing (AM) is certainly changing the space industry and providing new opportunities to travel to low earth orbit and explore our universe. New design opportunities –not previously possible –for new high performance metal alloys, light-weighting, managing thermal, structural, and dynamic loads are being enabled by AM. This presentation will showcase the vast portfolio of NASA’s AM activities in the last 12 years; transportation from Earth to Destination, Habitat at Destination, Lander from Station to Surface, and Science mission spacecrafts. NASA’s technical excellence is being leveraged heavily in the AM community thru collaborative projects, partnership agreements, tech transfer program. Challenges as well as opportunities will be discussed.

Alison Park↗

Technology Drives Exploration: How NASA Is Embracing Additive Manufacturing

NASA has over 60 years of technology development that enabled human space and space science exploration “for the benefit of all humankind”. This presentation will start with the overview of NASA’s organization structure; the roles NASA’s leadership plays as well as 10 regional centers’ focused areas and capabilities. It will also highlight NASA’s Mission Directorates –Science, Human, Aeronautics, and Technology. With the onset of the newer and still evolving procurement business model (NASA being a buyer, instead of maker), a question remains: which is the right framework under which NASA can best integrate the capabilities of commercial, international, and other US government entities into a coherent exploration strategy? Another critical consideration is identifying which critical technologies to invest in NASA and which capabilities are better suited for commercialization as NASA as a buyer. Additive Manufacturing (AM) is certainly changing the space industry and providing new opportunities to travel to low earth orbit and explore our universe. New design opportunities –not previously possible –for new high performance metal alloys, light-weighting, managing thermal, structural, and dynamic loads are being enabled by AM. This presentation will showcase the vast portfolio of NASA’s AM activities in the last 13 years; transportation from Earth to Destination, Habitat at Destination, Lander from Station to Surface, and Science mission spacecrafts. NASA’s technical excellence is being leveraged heavily in the AM and Commercial Space community through collaborative projects, partnership agreements, tech transfer program. Examples of challenges of AM implementation as well as opportunities will be discussed.

Alison Park↗

Additive Manufactured Hardware Qualification and Certification at NASA

Additive Manufacturing (AM) is certainly changing the space industry and providing new opportunities to travel to low earth orbit and explore our universe New design opportunities –not previously possible –for new high performance metal alloys, light-weighting, managing thermal, structural, and dynamic loads are being enabled by AM. Additively manufactured parts are already being inserted for complext system for NASA programs in critical applications –“ready to fly” Human exploration of space, especially deep space, requires extreme reliability Qualification of AM design/parts/process and Flight Certification

Alison Park↗

Ducted Fuel Injection And Cooled Spray Technologies For Particulate Control In Heavy-duty Diesel Engines (Final Report)

Cooled Spray (CS) and Ducted Fuel Injection (DFI) are in-cylinder technologies for diesel engines that can reduce particulate matter and soot emissions and data has been published showing that these technologies can reduce soot emissions by 75-100% for some engines at some operating conditions. However, little is known about scaling the devices for engine size. Additionally, the performance of either technology over the engine duty cycle has not been explored. This project addresses both of these points through single-cylinder engine investigations. The objectives of this project are to provide details about dimensional scaling of these devices and to demonstrate 75% PM reduction over a range of operating conditions on a single-cylinder engine. Two engines were used for this project: a 125mm bore optically accessible engine at Sandia National Laboratories and a 168mm bore metal engine at Southwest Research Institute. The optical engine was used to study the performance of DFI and CS inserts for a large injector orifice diameter injector that is characteristic of a locomotive engine and to perform scaling studies for DFI. The metal engine was used to perform scaling and alignment studies for CS and to evaluate the technology for both EGR and non-EGR engines over the engine operating map. Modifications were required for both engines to accept the prototype inserts being tested. The optical engine required a new fuel injector, cylinder head and piston so that tests could be run at the pressures and engine speeds required. Additionally, a novel rotating stage was designed for the optical engine to simplify alignment of the modules. The metal engine required a modified cylinder head to accept CS inserts and a modified piston to provide additional space around the fuel injector for the CS inserts. Tests on the optical engine showed that DFI reduces PM emissions for both small injector orifices (0.170mm diameter) and large injector orifices (0.290mm). For high load testing, the DFI modules were not as effective as at low load testing, but it was acknowledged that minimal geometric optimization was performed and more improvements may be possible. Comparing DFI to CS and conventional diesel combustion (CDC), DFI performed better than CS or CDC. The CS geometries used in these studies may not be ideal for that engine and additional modifications likely would improve performance. Tests on the metal engine showed PM reductions as high has 80% at some operating conditions with duty-cycle PM reductions of ~50% for EGR and non-EGR configurations. The CS testing on the metal engine showed that chamfering of the fuel passage inlet either through hydro-erosion or mechanical grinding provided significant improvements in the PM reduction capabilities of the insert. Additionally, alignment sensitivities were explored and the data show that the tolerance to misalignment is approximately 0.05 to 0.1mm for the inserts that were studied here. Air-fuel ratio was shown to be important in the effectiveness of the CS inserts. In several tests, it was shown that the CS inserts are more effective at reducing the PM for high-AFR operating conditions compared to low AFR conditions. In summary, multiple designs were evaluated on both engines. It was found that for the conditions and configurations studied here, a fuel passage diameter of ~2.5mm performed best overall. Significant duty-cycle PM reductions are possible using these technologies and sensitivities to AFR, alignment fuel passage diameter and inlet fuel passage shaping were explored and are reported here. More PM reduction may be possible with improved geometric design and attention to alignment practices.

02 PETROLEUM↗

Dual-Purpose Canister Filling Demonstration Project Progress Report at ORNL, 2023

The US DOE Office of Nuclear Energy is investigating the feasibility of direct disposal of dual-purpose canisters (DPCs) in a hypothetical geological repository to offset the potential requirement to repackage spent nuclear fuel (SNF) from existing DPCs into smaller, disposal-ready canisters. Oak Ridge National Laboratory (ORNL) is currently evaluating the feasibility of filling void space in loaded DPCs with an engineered material to prevent a criticality event caused by groundwater/moderator intrusion. Metal alloys are being investigated as a filler material because of their relatively low viscosities when molten, which may facilitate their injection via an existing drainpipe that runs almost the full length of the DPC. ORNL’s strategy for evaluating filler viability includes simulations and physical demonstrations of filling and casting behavior, as well as evaluations of materials for compatibility in the repository environment. Filling of DPCs in this manner is expected to mitigate the risk associated with a post-closure criticality event during the repository performance assessment time frame (10,000 years or greater). Efforts in this fiscal year focused on (1) destructive analysis of experimental filler castings made in FY 2022, (2) a report outlining a conceptual design of a DPC filling facility (Fortner et al., 2023, M3SF 23OR010305044/ ORNL/SPR-2023/2921, May 31, 2023), (3) a report on affected features, events, and processes (FEPs) due to DPC filling (Price et al., 2023, M3SF-23SN010305093, issuance pending), (4) developing and testing a more practical alloy filler based upon a Sn-Al eutectic, and (5) modeling the heating and cooling dynamics of a DPC subjected to molten metal filling. The preliminary results from each of these tasks support the feasibility of filling DPCs with metal as a strategy against the possibility of criticality in the repository. The FY 2022 casting was found to penetrate even very small orifices in the mold and internal structures. Preliminary testing of the Sn-Al eutectic indicate little interaction of the melt with Zircaloy cladding. Thermal modelling shows that a filled DPC will cool to manageable temperatures within 2-3 days, which is likely manageable in a facility.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Transformational Sorbent System for Post-Combustion Carbon Capture (Final Report)

As part of this DOE Contract (Transformational Sorbent System for Post-Combustion Carbon Capture, DE-FE0031734),TDA Research Inc. developed a transformational sorbent system for post combustion CO 2 capture process that captures more than 95% of CO 2 emissions from a coal fired power plant, recovering CO 2 at 95% purity with a cost of CO 2 capture significantly lower than with amine-based system (~$30 per tonne (MT) of CO 2 captured). TDA’s transformational sorbent system uses a novel, highly stable, high-capacity metal organic framework (MOF) based CO 2 sorbent in a new vacuum/concentration swing adsorption (VCSA) process that allows us to use high efficiency vacuum pumps with a low auxiliary load. A pulverized coal fired power plant equipped with TDA’s transformational sorbent system for post combustion CO 2 capture is expected to efficiently produce electricity with a low Cost of Electricity (COE) and capture greater than 95% of the CO 2 from the power plant exhaust.

01 COAL, LIGNITE, AND PEAT↗

Friction at small displacement.

Low contact resistance between metal surfaces is often observed in spite of interposed lubricant and/or oxide films. To study this effect an apparatus is used with which normal force and tangential microdisplacement are applied between a small lead rider and a gold flat with various surface film conditions. Under nonoxidized and nonlubricated conditions, and with either oxide or stearic acid lubricant film alone, friction is high and contact resistance is low. With oxide and lubricant together, friction is much lower and slide is smooth, but contact resistance remains low and Ohm's law is obeyed. The results are consistent with Greenwood's theory of contact resistance for a cluster of minute metallic contact spots within the load-supporting area. The contact resistance of such a cluster is indistinguishable, for practical purposes, from that given by complete metallic contact.

Campbell, W. E.↗

Low-Thermal-Stress Structural Joints For Dissimilar Materials

Structural joint developed for attachment of hypersonic control surface to aircraft wing structure. Transmits large torque loads from composite control surface and torque tube to wing structure through metallic attachment lug and collar. Torque load transmitted from tube to collar by series of radially oriented cleats. Bearing surfaces of cleats plane passing through center-line of torque tube. Such joints accommodate differential thermal growth between parts of dissimilar materials. Potential for application to high-temperature structural joints associated with hypervelocity vehicles.

Matza, Edward C.↗

Integrity of Ceramic Parts Predicted When Loads and Temperatures Fluctuate Over Time

Brittle materials are being used, and being considered for use, for a wide variety of high performance applications that operate in harsh environments, including static and rotating turbine parts for unmanned aerial vehicles, auxiliary power units, and distributed power generation. Other applications include thermal protection systems, dental prosthetics, fuel cells, oxygen transport membranes, radomes, and microelectromechanical systems (MEMS). In order for these high-technology ceramics to be used successfully for structural applications that push the envelope of materials capabilities, design engineers must consider that brittle materials are designed and analyzed differently than metallic materials. Unlike ductile metals, brittle materials display a stochastic strength response because of the combination of low fracture toughness and the random nature of the size, orientation, and distribution of inherent microscopic flaws. This plus the fact that the strength of a component under load may degrade over time because of slow crack growth means that a probabilistic-based life-prediction methodology must be used when the tradeoffs of failure probability, performance, and useful life are being optimized. The CARES/Life code (which was developed at the NASA Glenn Research Center) predicts the probability of ceramic components failing from spontaneous catastrophic rupture when these components are subjected to multiaxial loading and slow crack growth conditions. Enhancements to CARES/Life now allow for the component survival probability to be calculated when loading and temperature vary over time.

Nemeth, Noel N.↗

Cobalt-Catalyzed Hydrogenation Reactions Enabled by Ligand-Based Storage of Dihydrogen

The use of supporting ligands that can store either protons or electrons has emerged as a powerful strategy in catalysis. While these strategies are potent individually, natural systems mediate remarkable transformations by combining the storage of both protons and electrons in the secondary coordination sphere. As such, there has been recent interest in using this strategy to enable fundamentally different transformations. Furthermore, outsourcing H-atom or hydrogen storage to ancillary ligands can also enable alternative mechanistic pathways and thereby selectivity. Here, we describe the application of this strategy to facilitate radical reactivity in Co-based hydrogenation catalysis. Metalation of previously reported dihydrazonopyrrole ligands with Co results in paramagnetic complexes, which are best described as having Co(II) oxidation states. These complexes catalytically hydrogenate olefins with low catalyst loadings under mild conditions (1 atm H 2 , 23 °C). Mechanistic, spectroscopic, and computational investigations indicate that this system goes through a radical hydrogen-atom transfer (HAT) type pathway that is distinct from classic organometallic mechanisms and is supported by the ability of the ligand to store H 2 . These results show how ancillary ligands can facilitate efficient catalysis, and furthermore how classic organometallic mechanisms for catalysis can be altered by the secondary coordination sphere.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Quench in an Electrostatic Levitator

The Electrostatic Levitation (ESL) Laboratory at the NASA Marshall Space Flight Center (MSFC) is a unique facility for investigators studying high-temperature materials. The ESL laboratory’s main chamber has been upgraded with the addition of a rapid quench system. This system allows samples to be dropped into a quench vessel that can be filled with a low melting point material, such as a gallium or indium alloy, as a quench medium. Thereby allowing rapid quenching of undercooled liquid metals. Up to eight quench vessels can be loaded into a wheel inside the chamber that is indexed with control software. The system has been tested successfully with samples of zirconium, iron-cobalt alloys, iron-chromium-nickel, titanium-zirconium-nickel alloys, and a silicon-cobalt alloy. This new rapid quench system will allow materials science studies of undercooled materials and new materials development. The system is described and some initial results are presented.

SanSoucie, Michael P.↗

Rapid Quench in an Electrostatic Levitator

The Electrostatic Levitation (ESL) Laboratory at the NASA Marshall Space Flight Center (MSFC) is a unique facility for investigators studying high-temperature materials. The ESL laboratory's main chamber has been upgraded with the addition of a rapid quench system. This system allows samples to be dropped into a quench vessel that can be filled with a low melting point material, such as a gallium or indium alloy, as a quench medium. Thereby allowing rapid quenching of undercooled liquid metals. Up to eight quench vessels can be loaded into a wheel inside the chamber that is indexed with control software. The system has been tested successfully with samples of zirconium, iron-cobalt alloys, titanium-zirconium-nickel alloys, and a silicon-cobalt alloy. This new rapid quench system will allow materials science studies of undercooled materials and new materials development. In this presentation, the system is described and some initial results are presented.

SanSoucie, Michael P.↗

Design optimization of lightweight automotive seatback through additive manufacturing compression overmolding of metal polymer composites

With the growing demand for enhanced automotive fuel efficiency and environmental sustainability, there is a need for lightweighting automotive components through innovative design and manufacturing processes. Here, this study leverages a combination of numerical iterative design optimization and hybrid additive manufacturing–compression molding (AM-CM) technique for metal polymer composites to lightweight an automotive seatback. The AM-CM process enables robust mechanical interlocking between metals and composites, boasting high stiffness and strength with low overall density. Replacing metallic components with such metal polymer composites allows for comparable mechanical performance while significantly reducing the overall weight. First, the automotive seatback design space is reduced to critical load carrying regions using topology optimization and high stress concentration areas are identified using finite element analysis. Next, a lightweight metal polymer subcomponent is designed for a high stress concentration region. The full seatback frame with spatially heterogeneous material-specific design is then iteratively optimized to enable enhanced stiffness with minimal weight. Overall, the automotive seatback frame designed with location-specific metal, polymer, and metal polymer composite materials weighs 20% less than the metal-only design while exhibiting similar stiffness.

36 MATERIALS SCIENCE↗

Si Microwire-Array Photocathodes Decorated with Cu Allow CO 2 Reduction with Minimal Parasitic Absorption of Sunlight

High loadings of Cu were integrated on the light-facing side of Si microwire arrays used under simulated sunlight for the photoelectrochemical reduction of CO 2 (aq) to hydrocarbons in 0.10 M KHCO 3 (aq). Radial-junction n + p-Si microwire arrays decorated with Cu exhibited absolute photocurrent densities comparable to an uncovered Si surface. Moreover, with respect to a Cu foil electrode, the positive shift in the onset potential for hydrocarbon formation at n + p-Si/Cu microwire arrays was equal to or greater than the photovoltage of the semiconductor alone. Selective electrodeposition of Cu on the tips and sidewalls of Si microwires was responsible for the minimal parasitic reflection and absorption exhibited by the catalyst, such that light-limited, absolute current densities >25 mA·cm –2 were sustained for 48 h under simulated sunlight. Photoelectrodes prepared from semiconductors with low diode quality factors and electrocatalysts with large Tafel slopes are shown to benefit from increased microstructured surface area. Si microwire arrays are thus suitable for photoelectrochemical reactions requiring high loadings of metallic and reflective electrocatalysts.

25 ENERGY STORAGE↗