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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 37 records · Page 2

Mechanistic Studies of Continuous Partial Methane Oxidation on Cu−Zeolites Using Kinetic and Spectroscopic Methods

Abstract Over the past few decades, a significant amount of research effort has focused on investigating the active site requirements and reaction mechanisms for partial methane oxidation (PMO) to methanol over copper–exchanged zeolites during stoichiometric and stepwise chemical looping routes. More recently, research efforts have expanded to include investigating the PMO reaction in a continuous catalytic regime, primarily focusing on determining the influence of catalyst composition on Cu speciation and structure and, in turn, on PMO rate and selectivity. The structures of candidate Cu active sites are commonly studied using a combination of ex situ and in situ spectroscopic approaches. In this perspective, we critically examine the prior literature on catalytic PMO over Cu–zeolites to identify key knowledge gaps that remain in our understanding as motivation for future research efforts. We identify opportunities for future research to address these gaps by adapting analogous interrogation techniques that have been successfully used to elucidate the active site requirements and mechanistic details of another catalytic redox reaction cycle on Cu–zeolites, the selective catalytic reduction (SCR) of nitrogen oxides (NO x ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper-dependent halogenase catalyses unactivated C−H bond functionalization

Carbon–hydrogen (C–H) bonds are the foundation of essentially every organic molecule, making them an ideal place to do chemical synthesis. The key challenge is achieving selectivity for one particular C(sp 3 )−H bond. In recent years, metalloenzymes have been found to perform C(sp 3 )−H bond functionalization. Despite substantial progresses in the past two decades, enzymatic halogenation and pseudohalogenation of unactivated C(sp 3 )−H—providing a functional handle for further modification—have been achieved with only non-haem iron/α-ketoglutarate-dependent halogenases, and are therefore limited by the chemistry possible with these enzymes. Here, in this work, we report the discovery and characterization of a previously unknown halogenase ApnU, part of a protein family containing domain of unknown function 3328 (DUF3328). ApnU uses copper in its active site to catalyse iterative chlorinations on multiple unactivated C(sp 3 )−H bonds. By taking advantage of the softer copper centre, we demonstrate that ApnU can catalyse unprecedented enzymatic C(sp 3 )−H bond functionalization such as iodination and thiocyanation. Using biochemical characterization and proteomics analysis, we identified the functional oligomeric state of ApnU as a covalently linked homodimer, which contains three essential pairs—one interchain and two intrachain—of disulfide bonds. The metal-coordination active site in ApnU consists of binuclear type II copper centres, as revealed by electron paramagnetic resonance spectroscopy. This discovery expands the enzymatic capability of C(sp 3 )−H halogenases and provides a foundational understanding of this family of binuclear copper-dependent oxidative enzymes.

biocatalysis↗

Transition in helium bubble strengthening of copper from quasi-static to dynamic deformation

Damage from low-temperature irradiation and the subsequent degradation of materials performance pose significant challenges for the storage of radioactive materials and for peripheral components in some nuclear reactor designs. Fully understanding the mechanical behavior of such materials requires test data for strain rates in both the quasi-static (< 10/s) and dynamic (>> 10/s) regimes. While dynamic testing has generally been avoided in the past for neutron irradiated (contamination concerns) and ion irradiated (insufficient volume) materials, surface-sensitive Richtmyer-Meshkov instability (RMI) tests were used in the present work to overcome these limitations. Here, nanopillar compression, nanoindentation, and RMI testing data from a helium implanted surface layer (~10 µm thick) were compiled to explore the effects of helium bubbles on the materials strength of high-purity copper at strain rates of 0.001/s – 10 8 /s. While nano-mechanical testing revealed increases in yield strength and hardness with increasing helium dose from 1000 to 4000 appm He, RMI indicated no significant changes in strength as compared to unimplanted copper. Here, this discrepancy in behavior was rationalized through a combination of recent literature and follow-on molecular dynamics (MD) simulations, leading to the conclusion that the nanoscale helium bubbles acting as dispersed barriers to dislocation motion at quasi-static strain rates collapse under shock loading and cease to be effective barriers at high strain rates.

36 MATERIALS SCIENCE↗

Reduction of Ultrafine Hematite for a Spouting Bed Chemical Looping Process - Presentation

Chemical looping combustion research has been a topic of great interest since the mid-1990s, although the concept can be traced much further back. It is a combustion technology for fuel utilization that uses a two-reactor system to produce a carbon free effluent stream from the air reactor and a carbon dioxide rich stream from the fuel reactor with oxygen shuttled between the reactors with an oxygen carrier. Chemical looping combustion has been studied extensively because of this inherent separation of the carbon dioxide combustion product from the atmospheric nitrogen over that past 25 years with hundreds of research papers and tens of books. The oxygen carrier is, in general, a solid such as naturally occurring hematite or an engineered carrier like a copper and iron oxide supported on alumina. System technical and economic research activities conducted at the National Energy Technology Laboratory have shown that the costs associated with the carrier, initial and replacement, are a significant factor in the economic viability of the technology. To overcome this economic challenge, the work reported on in this paper investigates the use of a waste iron oxide as the chemical looping oxygen carrier. This waste material is quite unique as it has a particle size of 0.7 um. Given the particle size, the reactions are quite fast. However, the development of a contactor reactor to mix the fuel with the carrier is a fluidization challenge as the material is a Geldart group C material and highly cohesive. Normally, Geldart group C materials are fluidized with either a vibrating bed. This technique is acceptable for low temperature pharmaceuticals production but does not lend itself to much larger reactors used for power production or operation at temperatures in the order of 1100 to 1200 C. Therefore, a hydrodynamic solution was needed to break up the cohesive structures to replace the vibration. In this instance, it was hypothesized that a spouting bed of large Geldart group B or Geldart group D particles could provide the necessary energy to break up the cohesive structures of the Geldart group C material. This paper presents the reduction performance for this novel carrier material in a laboratory spouting bed reactor.

Breault, Ronald↗

Major Drivers of Long-Term Distribution Transformer Demand

Distribution transformers, used to step-down medium voltage to service-voltage level for end-use electrical consumption, are currently experiencing major shortages. Utilities are experiencing extended lead times for transformers of up to 2 years (a 4x increase on lead times pre-2022) and prices have gone up by as much as 5-6 times in the past 2 years. Current shortages have been attributed to pent-up post-pandemic demand, workforce shortages and low retention rates, component supply chain challenges, and materials shortages (grain-oriented electrical steel, aluminum, and copper). The supply of this equipment is critical for the reliability and growth of the power system, and in meeting administration climate goals in terms of electrification of demand and the growth of renewable energy. This report details some of the initial analysis conducted by the National Renewable Energy Laboratory (NREL), supported by the Department of Energy's Office of Electricity and Office of Policy, in assessing the long-term demand trends for distribution transformers. Expected increased demand is due to a confluence of not only electrification and renewable energy growth, but also in the context of aging electric infrastructure, increased frequency and severity of extreme weather events, and utility-driven investments in reliability and resiliency of the electricity distribution system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Heavy neutral leptons at beam dump experiments of future lepton colliders

A new beam dump experiment that utilizes the beam of future high energy electron-positron colliders could be an excellent avenue to search for dark sector particles due to its unprecedented high energy and intensity. We consider heavy neutral leptons (HNLs) as a specific example to demonstrate the sensitivity of searches for dark sector particles at future electron-positron collider beam dump experiments. This includes the study of the reach at the International Linear Collider (ILC), the Cool Copper Collider (C 3 ), and the Compact Linear Collider (CLIC). We comprehensively examine the HNL production and detector acceptance at these electron beam dump experiments. We show that these experiments will probe regions of HNL parameter space, not yet probed by past experiments, as well as by future approved experiments. Our study also motivates a more detailed analysis of heavy meson productions in high-energy electron-nucleon collisions in thick targets.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

London Penetration Depth Measurements Using Tunnel Diode Resonators

The London penetration depth λ is the basic length scale for electromagnetic behavior in a superconductor. Precise measurements of λ as a function of temperature, field and impurity scattering have been instrumental in revealing the nature of the order parameter and pairing interactions in a variety of superconductors discovered over the past decades. Here we recount our development of the tunnel-diode resonator technique to measure λ as function of temperature and field in small single crystal samples. Furthermore, we discuss the principles and applications of this technique to study unconventional superconductivity in the copper oxides and other materials such as iron-based superconductors. The technique has now been employed by several groups world-wide as a precision measurement tool for the exploration of new superconductors.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Unveiling the Influence of Carbon Impurity on Recovered NCM622 Cathode Material

With the proliferation of market demand for lithium-ion batteries (LIBs) over the past decades, battery recycling has aroused extensive attention due to the environmental, supply, and economic issues caused by waste batteries. Here, the hydrometallurgical recycling method has been widely adopted to recover cathode materials as a result of its wide applicability and high productivity. However, it is hard to completely eliminate impurities such as copper, aluminum, and carbon, which could bring significant impacts on recovered materials. Here, the influence of the carbon impurity on recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathode material is systematically investigated. It shows that the carbon impurity promotes nucleation during coprecipitation and forms holes in the cathode secondary particles after sintering which could enhance cyclability of the NCM622 cathode. The cathode with 0.2 atom % of carbon impurity displays the highest capacity of 159.9 mAh/g with a striking capacity retention rate of 97.9% after 100 cycles at 0.33C, but performs worse at high rates. Nonetheless, excess carbon (5 atom %) results in severe cation disorder and lattice distortion which significantly deteriorates the electrochemical properties of the NCM622 cathode. Therefore, it is important to strictly control carbon impurity during the recycling process for spent LIBs.

25 ENERGY STORAGE↗

Power Electronics Materials and Bonded Interfaces - Reliability and Lifetime

The need for reliable bonded interface materials is critical to realize the performance benefits of wide-bandgap devices in power electronic modules, especially in operating temperatures greater than 150 degrees Celsius. In this paper, we investigate the thermomechanical performance of sintered copper (Cu) as a large-area attachment, bonded between Cu baseplates and active-metal-bonded substrates, under accelerated thermal shock (-40 degrees Celsius to 200 degrees Celsius) conditions. In the fabrication phase of the samples, we used different stencil patterns and found out that the grid and stripe patterns resulted in a better outgassing of the residual organics during the sintering process, thereby ensuring a substantially improved bond quality than a full-area print. The paste consisted of Cu microflakes and we performed sintering using a Budatec SP300 sintering press at 275 degrees Celsius with 15 MPa of bonding pressure for 5 minutes in a nitrogen atmosphere. Under accelerated experiments, we monitored the degradation of the sintered Cu bond in the samples through C-mode scanning acoustic microscope (C-SAM) images. To quantify the defect percentage in C-SAM images, we investigated image denoising techniques to exclude the pattern prints. Finally, we cross-sectioned a sample and obtained digital microscope images, which revealed adhesive fracture as the dominant failure mechanism.

ADVANCED PROPULSION SYSTEMS↗

A New Era for Bubble Chamber Technology

Neutrino experiments like DUNE are limited by how well we understand the way neutrinos actually interact with atoms. The best way to fix that is to measure interactions on hydrogen, since a hydrogen nucleus is just a single free proton with largely none of the nuclear effects that heavier targets like argon have. The catch is that no one has built a hydrogen bubble chamber for a neutrino beam since the 1980s, mostly because the old chambers had too low of an active time. MAMBA is a project focused on bringing that technology back but built to cycle continuously at 1 Hz. I spent my summer internship on two of the subsystems that make that kind of speed possible. First, I helped install and test a new solid copper thermal link that replaced the old flexible braided cooling path, and it brought the coldhead down to 21.3 K, right at the target temperature. Second, I built and tested a Raspberry Pi based PLC control system, and across 20,000 trials it answered in a median of 0.64 ms, with only 0.66\% of trials running past 1 ms. Both results point the same direction: that inexpensive, off the shelf hardware can perform fast and reliable enough to eventually run a bubble chamber the way MAMBA needs it to run.

Williams, Nicholas [DuPage Coll.]↗

Improved internal short circuit models for thermal runaway simulations in lithium-ion batteries

Thermal runaway (TR) modeling is one of the primary tools that can be used to overcome challenges associated with lithium-ion battery (LIB) safety. Among all LIB accidents that have occurred over the past decade, Internal Short Circuit (ISC) remains the most common trigger mechanism. Many available models in the literature either use a simplified approach to simulate ISC or completely ignore its contribution. The aim of this study is to understand the nature of the heat released for different types of ISC scenarios, including aluminum-anode, anode–cathode, and copper-cathode ISC. We study ISC behavior using a coupled electrochemical–thermal model with an integrated TR chemical kinetics solver built in the COMSOL Multiphysics framework. The time duration of heat release and the magnitude of the peak ISC current are studied as functions of parameters such as the size of the penetrating filament and the capacity of the cell. The numerical results are used to build an empirical model validated against the published experimental TR propagation data. Our model can be successfully used as a viable low-cost substitute in lower order (lumped) TR simulations to enable TR prevention and mitigation.

Singh, Bakhshish Preet (ORCID:0000000264751992)↗

Surrogate Assembly 30 cm Drop Test

The 30 cm drop is the remaining NRC normal conditions of transport (NCT) regulatory requirement (10 CFR 71.71) for which there are no data on the actual surrogate fuel. While obtaining data on the actual fuel is not a direct requirement, it provides definitive information which aids in quantifying the risk of fuel breakage resulting from a cask drop from a height of 30 cm or less. The 30 cm drop test with the full-scale surrogate assembly conducted in May 2020 was the last step needed for quantifying the strains on the surrogate assembly rods under NCT. The full-scale surrogate assembly used in the 2020 30 cm drop test was built using a new 17x17 Pressurized Water Reactor (PWR) Westinghouse skeleton filled with the copper rods and 3 zircaloy rods from the full-scale surrogate assembly used in the Multi-Modal Transportation Test (MMTT). Felt pads were attached to the surrogate assembly bottom prior to the 30 cm drop to adequately represent the effects of the impact limiters and the cask. Note that felt "programming material" has been used extensively in past drop tests and is known to be a good material for programming a desired shock pulse. The felt pad configuration was determined during a previous series of tests reported in. The acceleration pulses observed on the surrogate assembly during the test were in good agreement with the expected pulses. This confirmed that during the 30 cm drop the surrogate assembly experienced the same conditions as it would if it was dropped in the cask with the impact limiters.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The effect of neutron irradiation on conventional and nanocrystalline nickel: NSUF Work Package UA-22PN080501 Milestone M3UA-22PN0805012 (Final Report)

Even though nanocrystalline materials (20-100 nm) present an unprecedented potential, scientific knowledge related to the effect of neutron irradiation on the mechanical properties and microstructure is still scarce. Most of the past studies were conducted using ion irradiation which may not have the same effect as neutron irradiation because of the smaller irradiation volume and the higher dose rate. To reach a firm conclusion on the potential of nanocrystalline materials for nuclear reactor applications, extensive study of model metals with different stacking fault energy (SFE) is required to elucidate their behavior in radiation environments. Nanocrystalline copper and nickel are typically chosen because they are commonly used as model FCC metals in studies of radiation effects. Nickel is an FCC metal with a high stacking-fault energy (~125 mJ/m 2 ) compared to copper (~45 mJ/m 2 ). Hence, microcrystalline and nanocrystalline nickel samples were irradiated in the INL’s Advanced Test Reactor (ATR), as a part of FY08 North Carolina State University NSUF Irradiation Experiment# 96 to evaluate the irradiation behavior of these materials. The objective of this FY20 NSUF project# 19122 is to perform PIE (at PNNL NSUF facility) on previously ATR-neutron irradiated (1.2 and 2.6 dpa; 80-89°C) nanocrystalline and microcrystalline nickel samples to investigate the changes in mechanical properties and microstructures and evaluate whether nanocrystalline nickel is relatively more radiation resistant compared to conventional microcrystalline nickel. To perform PIE at PNNL, sixteen neutron irradiated specimens (microcrystalline and nanocrystalline) were transferred from the NSUF Nuclear Fuels and Materials Library at INL. Experimental techniques such as SEM/EBSD, XRD, TEM, Vickers microhardness and tensile testing were employed to characterize the effect of neutron irradiation on the microstructure and mechanical properties of nanocrystalline nickel and compared them with corresponding characteristics of microcrystalline nickel.

36 MATERIALS SCIENCE↗

Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores

For the past eleven years, a dedicated effort in our research group focused on fundamentally advancing the photophysical properties of cuprous bis-phenanthroline-based metal-to-ligand charge transfer (MLCT) excited states. We rationalized that by gaining control over the numerous factors limiting the more widespread use of Cu I MLCT photosensitizers, they would be readily adopted in numerous light-activated applications given the earth-abundance of copper and the extensive library of 1,10-phenanthrolines developed over the last century. Significant progress has been achieved by recognizing valuable structure-property concepts developed by other researchers in tandem with detailed ultrafast and conventional time-scale investigations, in-silico-inspired molecular designs to predict spectroscopic properties, and applying novel synthetic methodologies. Ultimately, we achieved a plateau in exerting cooperative steric influence to control Cu I MLCT excited state decay. This led to combining sterics with π-conjugation and/or inductive electronic effects to further exert control over molecular photophysical properties. The lessons gleaned from our studies of homoleptic complexes were recently extended to heteroleptic bis(phenanthrolines) featuring enhanced visible light absorption properties and long-lived room-temperature photoluminescence. Furthermore, this Account navigates the reader through our intellectual journey of decision-making, molecular and experimental design, and data interpretation in parallel with appropriate background information related to the quantitative characterization of molecular photophysics using Cu I MLCT chromophores as prototypical examples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Deciphering electrocatalysts with multimodal operando approaches

Here, the electrocatalytic processes of a copper catalyst during nitrate electroreduction are unveiled by correlated operando microscopy and spectroscopy. Catalysts are vital to the modern chemical industry, yet their development has largely relied on trial-and-error approaches. Optimizing catalysts requires a fundamental understanding of their structure–chemical property behaviour under operational conditions. However, operando characterization remains challenging, especially for reactions occurring in the complex and dynamic liquid environments of electrochemical systems. Over the past decade, the rapid development of in situ and operando environmental transmission electron microscopy (ETEM) and microelectromechanical system (MEMS)-based closed-cell holders, enabling environmental studies within the vacuum environment of transmission electron microscopy (TEM), has substantively advanced understanding of heterogeneous catalysis, notably for gas-phase reactions. In situ ETEM enables the direct observation of the catalyst evolution in terms of structure, morphology and chemical state at the nano-to-atomic scale, providing insights into their correlation with catalytic performance.

36 MATERIALS SCIENCE↗

Thermomechanical Degradation of Sintered Copper Under High-Temperature Thermal Shock

The need for reliable bonded interface materials is critical to realize the performance benefits of wide-bandgap devices in power electronics modules, especially in operating temperatures greater than 150 degrees C. In this paper, we investigate the thermomechanical performance of sintered copper (Cu) as a large-area attachment, bonded between Cu baseplates and active-metal-bonded substrates, under accelerated thermal shock (-40 degrees C to 200 degrees C) conditions. In the fabrication phase of the samples, we used different stencil patterns and found that the grid and stripe patterns resulted in a better outgassing of the residual organics during the sintering process, thereby ensuring a substantially improved bond quality compared to a full-area print. The paste consisted of Cu microflakes, and we performed sintering using a Budatec SP300 sintering press at 275 degrees C with 15 MPa of bonding pressure for 5 minutes in a nitrogen atmosphere. Under accelerated experiments, we monitored the degradation of the sintered Cu bond in the samples through C-mode scanning acoustic microscope (C-SAM) images. To quantify the defect percentage in C-SAM images, we investigated image denoising techniques to exclude the pattern prints. Finally, we cross-sectioned a sample and obtained scanning electron microscope images, which revealed adhesive fracture as the dominant failure mechanism.

ADVANCED PROPULSION SYSTEMS,INORGANIC, ORGANIC, PH↗

Past fires and post-fire impacts reconstructed from a southwest Australian stalagmite

Speleothem records of past environmental change provide an important opportunity to explore fire frequency and intensity in the past, and the antecedent climatic conditions leading to fire events. Here, fire sensitive geochemical signals in a stalagmite from Yonderup Cave, a shallow cave in Western Australia, are compared to well-documented wildfire events that occurred in recent decades. The results are extended to identify wildfires during the growth interval of the speleothem (1760 CE–2005 CE). Principal component analysis of the stalagmite time-series revealed distinct peaks in a combination of phosphorus and metal (aluminium, zinc, copper and lead) concentrations in response to known fire events, which are interpreted to have come from ash. Varying responses in the geochemical signal in the pre- and post-European colonisation period are likely linked to changes in land management, fire frequency and fire intensities. Of note is what we infer to be a particularly intense fire event concluded to have occurred in 1897 ± 5 CE, which climate sensitive proxies (δ18O and bedrock-derived elements) indicate was preceded by a multi-decadal dry period that began in the late 1860s. The intensity of the deduced fire event is supported by a peak in P that is 6.3 times higher than elsewhere in the speleothem, accompanied by a peak in Zn. It was also inferred that changes to the surface-cave hydrology occurred as a result of this event, indicated by increased input of colloidal organic material onto the stalagmite that was interpreted to be caused by shallow karst bedrock fracturing from the heat-induced deformation that is observed after intense fires. These findings show the potential for speleothems to provide dated records of fire intensity and recurrence intervals. Further development could lead to a better understanding of the climate-fire relationship and the effects of land-management practices on wildfire frequency and intensity.

58 GEOSCIENCES↗

Ultra-black coatings for space instruments: a comparison of traditional Ebonol C processes and a method for future repeatability

Ultra-black coatings have served various roles in space instrumentation and hardware. The Ebonol C coating has been used for various missions requiring low reflectivity on aluminum substrates that are electrically conducting. This coating is produced through the formation of a cupric oxide structure on an intermediate layer of copper applied to the aluminum. For many years, this commercial formulation has been used ubiquitously for space instruments. The coating relies upon details of the copper base layer that have been trade secret at various finishing companies, and the availability of the Ebonol C formulated chemistry from the chemical supplier. In recent years, this product has been discontinued at various times, leaving vendors to either rely on expired stock or to formulate their own equivalents. Here, we detail the processing methods, chemistries, and resultant coating structures that produce reflectance performance equivalent to baseline historical reflectance data. This process detail will ensure equivalent performance for such coatings for future missions and link the performance to past and currently deployed instruments.

36 MATERIALS SCIENCE↗