Search NASA⌕ Search

SEARCH · Search NASA

Results for “oxygen sensitivity”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Harnessing selenocysteine to enhance microbial cell factories for hydrogen production

Hydrogen is a clean, renewable energy source, that when combined with oxygen, produces heat and electricity with only water vapor as a biproduct. Furthermore, it has the highest energy content by weight of all known fuels. As a result, various strategies have engineered methods to produce hydrogen efficiently and in quantities that are of interest to the economy. To approach the notion of producing hydrogen from a biological perspective, we take our attention to hydrogenases which are naturally produced in microbes. These organisms have the machinery to produce hydrogen, which when cleverly engineered, could be useful in cell factories resulting in large production of hydrogen. Not all hydrogenases are efficient at hydrogen production, and those that are, tend to be oxygen sensitive. Therefore, we provide a new perspective on introducing selenocysteine, a highly reactive proteinogenic amino acid, as a strategy towards engineering hydrogenases with enhanced hydrogen production, or increased oxygen tolerance.

08 HYDROGEN↗
DOE OSTI2024

Nitrogen-Fixing Gamma Proteobacteria Azotobacter vinelandii—A Blueprint for Nitrogen-Fixing Plants?

The availability of fixed nitrogen limits overall agricultural crop production worldwide. The so-called modern “green revolution” catalyzed by the widespread application of nitrogenous fertilizer has propelled global population growth. It has led to imbalances in global biogeochemical nitrogen cycling, resulting in a “nitrogen problem” that is growing at a similar trajectory to the “carbon problem”. As a result of the increasing imbalances in nitrogen cycling and additional environmental problems such as soil acidification, there is renewed and increasing interest in increasing the contributions of biological nitrogen fixation to reduce the inputs of nitrogenous fertilizers in agriculture. Interestingly, biological nitrogen fixation, or life’s ability to convert atmospheric dinitrogen to ammonia, is restricted to microbial life and not associated with any known eukaryotes. It is not clear why plants never evolved the ability to fix nitrogen and rather form associations with nitrogen-fixing microorganisms. Perhaps it is because of the large energy demand of the process, the oxygen sensitivity of the enzymatic apparatus, or simply failure to encounter the appropriate selective pressure. Whatever the reason, it is clear that this ability of crop plants, especially cereals, would transform modern agriculture once again. Successfully engineering plants will require creating an oxygen-free niche that can supply ample energy in a tightly regulated manner to minimize energy waste and ensure the ammonia produced is assimilated. Nitrogen-fixing aerobic bacteria can perhaps provide a blueprint for engineering nitrogen-fixing plants. This short review discusses the key features of robust nitrogen fixation in the model nitrogen-fixing aerobe, gamma proteobacteria Azotobacter vinelandii, in the context of the basic requirements for engineering nitrogen-fixing plants.

Microbiology↗
DOE OSTI2022

Synechocystis sp. PCC 6803 Requires the Bidirectional Hydrogenase to Metabolize Glucose and Arginine Under Oxic Conditions

The cyanobacterium Synechocystis sp.PCC 6803 possesses a bidirectional NiFe-hydrogenase, HoxEFUYH. It functions to produce hydrogen under dark, fermentative conditions and photoproduces hydrogen when dark-adapted cells are illuminated. Unexpectedly, we found that the deletion of the large subunit of the hydrogenase (HoxH) in Synechocystis leads to an inability to grow on arginine and glucose under continuous light in the presence of oxygen. This is surprising, as the hydrogenase is an oxygen-sensitive enzyme. In wild-type (WT) cells, thylakoid membranes largely disappeared, cyanophycin accumulated, and the plastoquinone (PQ) pool was highly reduced, whereas ΔhoxH cells entered a dormant-like state and neither consumed glucose nor arginine at comparable rates to the WT. Hydrogen production was not traceable in the WT under these conditions. We tested and could show that the hydrogenase does not work as an oxidase on arginine and glucose but has an impact on the redox states of photosynthetic complexes in the presence of oxygen. It acts as an electron valve as an immediate response to the supply of arginine and glucose but supports the input of electrons from arginine and glucose oxidation into the photosynthetic electron chain in the long run, possibly via the NDH-1 complex. Despite the data presented in this study, the latter scenario requires further proof. The exact role of the hydrogenase in the presence of arginine and glucose remains unresolved. In addition, a unique feature of the hydrogenase is its ability to shift electrons between NAD(H), NADP(H), ferredoxin, and flavodoxin, which was recently shown in vitro and might be required for fine-tuning. Taken together, our data show that Synechocystis> depends on the hydrogenase to metabolize organic carbon and nitrogen in the presence of oxygen, which might be an explanation for its prevalence in aerobic cyanobacteria.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

A synthetic co-culture for bioproduction of ammonia from methane and air

Abstract Fixed nitrogen fertilizers feed 50% of the global population, but most fixed nitrogen production occurs using energy-intensive Haber–Bosch-based chemistry combining nitrogen (N2) from air with gaseous hydrogen (H2) from methane (CH4) at high temperatures and pressures in large-scale facilities sensitive to supply chain disruptions. This work demonstrates the biological transformation of atmospheric N2 into ammonia (NH3) using CH4 as the sole carbon and energy source in a single vessel at ambient pressure and temperature, representing a biological “room-pressure and room-temperature” route to NH3 that could ultimately be developed to support compact, remote, NH3 production facilities amenable to distributed biomanufacturing. The synthetic microbial co-culture of engineered methanotroph Methylomicrobium buryatense (now Methylotuvimicrobium buryatense) and diazotroph Azotobacter vinelandii converted three CH4 molecules to l-lactate (C3H6O3) and powered gaseous N2 conversion to NH3. The design used division of labor and mutualistic metabolism strategies to address the oxygen sensitivity of nitrogenase and maximize CH4 oxidation efficiency. Media pH and salinity were central variables supporting co-cultivation. Carbon concentration heavily influenced NH3 production. Smaller-scale NH3 production near dispersed, abundant, and renewable CH4 sources could reduce disruption risks and capitalize on untapped energy resources. One-Sentence Summary Co-culture of engineered microorganisms Methylomicrobium buryatense and Azotobacter vinelandii facilitated the use of methane gas as a sole carbon feedstock to produce ammonia in an ambient temperature, atmospheric pressure, single-vessel system.

Biotechnology & Applied Microbiology↗
DOE OSTI2026

Spin‐Polarized Interfaces Redirect CO 2 Reduction From CO to Formate

Achieving high product selectivity in electrocatalytic carbon dioxide reduction (CO 2 RR) remains a critical challenge due to competition between multiple proton-coupled electron-transfer pathways on catalyst surfaces. Meanwhile, chirality-induced spin selectivity (CISS), which enables spin-polarized electron transport through chiral interfaces, has recently emerged as a promising strategy to modulate interfacial electrochemical reactions. Although the CISS effect has been shown to enhance selectivity and efficiency in the spin-sensitive oxygen evolution reaction (OER), its role in regulating CO 2 RR pathways and in stabilizing intermediates remains largely unexplored. Here, chiral molecules (R- and S-1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, BNP) were integrated with SnO 2 to construct chiral-modified catalysts (R-BNP/SnO 2 and S-BNP/SnO 2 ). Compared with bare SnO 2 and racemic BNP-modified SnO 2 (Rac-BNP/SnO 2 ), the chiral catalysts exhibited a pronounced shift in product selectivity from CO toward formate production. Importantly, in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals that the chiral interface selectively stabilizes the O-bound *OCHO intermediate associated with the formate pathway and modulates interfacial water structure and hydrogen-bonding dynamics. These findings demonstrate that spin-polarized interfacial electron transfer can regulate CO 2 RR pathway selectivity by modulating the stabilization of key intermediates. More broadly, this work establishes chiral spin-selective interfaces as a new strategy for regulating competitive electrocatalytic reaction pathways.

14 SOLAR ENERGY↗
DOE OSTI2020

Caught in the H inact : Crystal Structure and Spectroscopy Reveal a Sulfur Bound to the Active Site of an O 2 -stable State of [FeFe] Hydrogenase

[FeFe] hydrogenases are the most active H 2 converting catalysts in nature, but their extreme oxygen sensitivity limits their use in technological applications. The [FeFe] hydrogenases from sulfate reducing bacteria can be purified in an O 2 -stable state called H inact . To date, the structure and mechanism of formation of H inact remain unknown. Our 1.65 Å crystal structure of this state reveals a sulfur ligand bound to the open coordination site. Furthermore, in-depth spectroscopic characterization by X-ray absorption spectroscopy (XAS), nuclear resonance vibrational spectroscopy (NRVS), resonance Raman (RR) spectroscopy and infrared (IR) spectroscopy, together with hybrid quantum mechanical and molecular mechanical (QM/MM) calculations, provide detailed chemical insight into the Hinact state and its mechanism of formation. This may facilitate the design of O 2 -stable hydrogenases and molecular catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

New approaches to secondary metabolite discovery from anaerobic gut microbes

The animal gut microbiome is a complex system of diverse, predominantly anaerobic microbiota with secondary metabolite potential. These metabolites likely play roles in shaping microbial community membership and influencing animal host health. As such, novel secondary metabolites from gut microbes hold significant biotechnological and therapeutic interest. Despite their potential, gut microbes are largely untapped for secondary metabolites, with gut fungi and obligate anaerobes being particularly under-explored. To advance understanding of these metabolites, culture-based and (meta)genome-based approaches are essential. Culture-based approaches enable isolation, cultivation, and direct study of gut microbes, and (meta)genome-based approaches utilize in silico tools to mine biosynthetic gene clusters (BGCs) from microbes that have not yet been successfully cultured. In this mini-review, we highlight recent innovations in this area, including anaerobic biofoundries like ExFAB, the NSF BioFoundry for Extreme & Exceptional Fungi, Archaea, and Bacteria. These facilities enable high-throughput workflows to study oxygen-sensitive microbes and biosynthetic machinery. Such recent advances promise to improve our understanding of the gut microbiome and its secondary metabolism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Highly tail-asymmetric lipids interdigitate and cause bidirectional ordering

Phospholipids form structurally and compositionally diverse membranes. A less studied type of compositional diversity involves phospholipid tail variety. Some phospholipids contain two acyl tails which differ in length. These tail-asymmetric lipids are shown to contribute to temperature sensitivity, oxygen adaptability, and membrane fluidity. Membranes of a highly virulent intracellular bacterium, Francisella tularensis, contain highly tail-asymmetric 1-lignoceroyl-2-decanoyl-sn-glycero-3-phosphatidylethanolamine (XJPE) lipids which were previously shown to inhibit inflammatory responses in host cells. XJPE tails have unusually high asymmetry, and how they contribute to membrane properties on a molecular level is unknown. Here, we use small angle X-ray scattering and molecular dynamics simulations to investigate how varying XJPE ratios alters properties of simple membranes. Our results demonstrate that at high concentration they promote liquid-to-gel transition in otherwise liquid membranes, while at low concentration they are tolerated well, minimally altering membrane properties. In liquid membranes, XJPE lipids dynamically adopt two main conformations; with the long tail extended into the opposing leaflet or bent-back residing in its own leaflet. When added to both leaflets XJPE primarily adopts an extended confirmation, while asymmetric addition results in more bent-back orientations. The former increases tail ordering and the latter decreases it. XJPE tails adopt different conformations that induce composition- and leaflet-dependent bidirectional effect on membrane fluidity and this suggests that Francisella tularensis could use tail asymmetry to facilitate vesicle fusion and destabilize host cells. The effect of tail-asymmetric lipids on complex membranes should be further investigated to reveal the regulatory roles of high tail asymmetry.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Unusual photophysical properties of a new tricyclic derivative of thiopurines in terms of potential applications

The thio analogues of purine bases have been found to possess notable biological and pharmacological capabilities and have an important role to play as anticancer and immunosuppressive drugs. In this work a new tricyclic analogue of guanosine containing sulfur was synthesized, in particular, DTEG (2',3',5'-tri-O-acetyl-6,9-dithioethanoguanosine). Although there is promise for thiopurine derivatives for biomedical applications, there are some liabilities in regard to their exposure to light. As a preliminary survey for such difficulties with DTEG, this work looks into spectral and photophysical processes of DTEG using time-resolved and steady-state optical excitation. In contrast to other thiopurines, which have long-lived triplets, DTEG is shown to have a short-lived triplet making it less dangerous for singlet-oxygen sensitization. Even in anaerobic solutions, its photoreactivity is negligible. These various unusual photochemical properties of DTEG are consistent with DTEG being very promising as an alternative drug to the currently used 6-thiopurines. DTEG also has some interesting photophysical behavior that is distinct from other thioketones. Although thioketones have an unusual fluorescence violating Kasha’s Rule and emitting from the second excited singlet state, DTEG does this also, but, in addition, it shows dual fluorescence by emitting from its first excited singlet as well. The assignments of the nature of these excited states are supported by DFT results. This theory and associated kinetic analysis show quantitatively that the dual fluorescence is, in part, tied to the relatively fast S 2 to S 1 internal conversion compared to other S 2 decays and, in part, tied to the relatively slow nonradiative decay of S 1 itself.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Synthesis, Redox, and Spectroscopic Properties of Pd(II) 10,10-Dimethylisocorrole Complexes Prepared via Bromination of Dimethylbiladiene Oligotetrapyrroles

Two brominated 10,10-dimethylisocorrole (10-DMIC) derivatives containing Pd(II) centers have been prepared and characterized. These compounds were prepared via bromination of 10,10-dimethylbiladiene-based oligotetrapyrroles. Bromination of free base 10,10-dimethylbiladiene (DMBil1) followed by metalation with Pd(OAc) 2 , as well as bromination of the corresponding Pd(II) dimethylbiladiene complex (Pd[DMBil1]) provide routes to Pd(II) hexabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br 6 ]) and Pd(II) octabromo-10,10-dimethyl-5,15-bis(pentafluorophenyl)-isocorrole (Pd[10-DMIC-Br 8 ]). The solid-state structures of the two brominated isocorrole complexes are presented, as is that for a new decabrominated dimethylbiladiene derivative (DMBil-Br 10 ). The electronic and spectroscopic properties of the brominated biladiene and isocorrole derivatives were probed using a combination of voltammetric methods and steady-state UV–vis absorption and emission experiments. Data obtained from these experiments allow the properties of the brominated biladiene and isocorrole derivatives to be compared to previously studied biladiene derivatives (i.e., DMBil1 and Pd[DMBil1]). CV and DPV experiments demonstrate that Pd[10-DMIC-Br 6 ] and Pd[10-DMIC-Br 8 ] support well-behaved multielectron redox chemistry, similar to that which has been observed for other nonaromatic tetrapyrroles containing sp 3 -hybridized meso-carbons. Here, spectroscopic experiments reveal that bromination of the dimethylbiladiene core shifts this system’s UV–vis absorption profile to lower energy and that the dimethylisocorrole complexes support panchromatic absorption profiles that extend across the UV–vis and into the near-IR region. Photosensitization experiments demonstrate that unlike previously studied Pd(II) biladiene constructs, DMBil-Br 10 , Pd[10-DMIC-Br 6 ], and Pd[10-DMIC-Br 8 ] support limited triplet excited state chemistry with O 2 , indicating that the novel nonaromatic tetrapyrrole derivatives described in this work may be best suited for applications other than singlet oxygen sensitization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Iron-sulfur clusters are involved in post-translational arginylation

Eukaryotic arginylation is an essential post-translational modification that modulates protein stability and regulates protein half-life. Arginylation is catalyzed by a family of enzymes known as the arginyl-tRNA transferases (ATE1s), which are conserved across the eukaryotic domain. Despite their conservation and importance, little is known regarding the structure, mechanism, and regulation of ATE1s. In this work, we show that ATE1s bind a previously undiscovered [Fe-S] cluster that is conserved across evolution. We characterize the nature of this [Fe-S] cluster and find that the presence of the [Fe-S] cluster in ATE1 is linked to its arginylation activity, both in vitro and in vivo, and the initiation of the yeast stress response. Importantly, the ATE1 [Fe-S] cluster is oxygen-sensitive, which could be a molecular mechanism of the N-degron pathway to sense oxidative stress. Taken together, our data provide the framework of a cluster-based paradigm of ATE1 regulatory control.

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

Toward a glycyl radical enzyme containing synthetic bacterial microcompartment to produce pyruvate from formate and acetate

Formate has great potential to function as a feedstock for biorefineries because it can be sustainably produced by a variety of processes that don’t compete with agricultural production. However, naturally formatotrophic organisms are unsuitable for large-scale cultivation, difficult to engineer, or have inefficient native formate assimilation pathways. Thus, metabolic engineering needs to be developed for model industrial organisms to enable efficient formatotrophic growth. Here, we build a prototype synthetic formate utilizing bacterial microcompartment (sFUT) encapsulating the oxygen-sensitive glycyl radical enzyme pyruvate formate lyase and a phosphate acyltransferase to convert formate and acetyl-phosphate into the central biosynthetic intermediate pyruvate. This metabolic module offers a defined environment with a private cofactor coenzyme A that can cycle efficiently between the encapsulated enzymes. To facilitate initial design-build-test-refine cycles to construct an active metabolic core, we used a “wiffleball” architecture, defined as an icosahedral bacterial microcompartment (BMC) shell with unoccupied pentameric vertices to freely permit substrate and product exchange. The resulting sFUT prototype wiffleball is an active multi enzyme synthetic BMC functioning as platform technology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Structure of active methyl-CoM reductase, Earth’s main methane producer

Summary Our work reveals the structure of the active state of Methyl-Coenzyme M Reductase (MCR), the key and rate-limiting enzyme in biological methane formation. We find large differences between the active Ni(I) and inactive Ni(II) proteins and provide insight into how nature makes and breaks the C-H bond of methane. The Ni(II)-F430 center in inactive MCR contains four planar nitrogen ligands, a lower axial glutamine oxo, and an upper axial thiolate. The Ni(I)-enzyme replaces the axial ligands with a single water. The one-electron redox change results in movement of the Ni ion and upward swing of the β-lactam ring in the tetrapyrrole coupled to a domino-like protein quake through second sphere residues, inter-subunit interactions, a substrate tunnel, affecting even the dimensions of the unit cell. These structural changes lead Ni(I)-MCR to release a charge clamp that, in the Ni(II) state, locks down substrate Coenzyme B. Determining the Ni(I)-MCR structure required development of rigorous anaerobic crystallographic techniques. Validation of the MCR redox state was accomplished by in-line and parallel spectroscopic and unit cell analyses. This structure has large implications for developing technologies to limit methane emissions and efficiently produce biofuels. Methodology described here will enhance structural biology for other oxygen-sensitive enzymes.

09 BIOMASS FUELS↗
DOE OSTI2025

Deletion of Re -citrate synthase allows for analysis of contributions of tricarboxylic acid cycle directionality to the growth of Heliomicrobium modesticaldum

ABSTRACT Heliomicrobium modesticaldum,a phototrophic member of the phylum Firmicutes and family Clostridiales, possesses most of the enzymes specific to the reductive tricarboxylic acid (rTCA) cycle, except for the key enzyme, ATP-citrate lyase. It is thought to utilize a split TCA cycle when growing on pyruvate as a carbon source, in which the oxidative TCA (oTCA) direction generates most of the 2-ketoglutarate, but some can be produced in the reductive direction. Although a typicalSi-citrate synthase gene is not found in the genome, it was suggested that gene HM1_2993, annotated as homocitrate synthase, actually encodesRe-citrate synthase, which would function as the initial enzyme of the oTCA cycle. We deleted this gene to test this hypothesis and, if true, see what effect severing access to the oTCA cycle would have on this organism. The endogenous CRISPR-Cas system was used to replace the open reading frame with a selectable marker. The deletion mutants could grow on pyruvate but were unable to grow phototrophically on acetate + CO 2 as carbon source. Growth on acetate could be rescued by the addition of different electron sources (formate or ascorbate), suggesting that the oTCA cycle is used to oxidize acetate to generate electrons required to drive the carboxylation of acetyl-CoA. The deletion mutants were capable of growing in acetate minimal media without additional organic supplements beyond formate, demonstrating that the rTCA cycle can be employed to support sufficient 2-ketoglutarate production in this organism, unlike citrate synthase mutants in several chemoheterotrophic organisms utilizing the oTCA cycle. IMPORTANCE Heliobacteria are a unique group of phototrophic bacteria that are obligate anaerobes and possess a rudimentary system to use light as a source of energy. They do not make oxygen or fix carbon dioxide. Here, we explore their fundamental carbon metabolism to understand the role and operation of the central TCA cycle. This work shows both the role and operation of this cycle under different growth modes and explains how these organisms can obtain electrons to drive their biosynthetic metabolism. This foundational knowledge will be crucial in the future when attempts are made to use this organism as a platform for oxygen-sensitive synthesis of compounds in an anaerobe that can use light as its energy source.

Biotechnology & Applied Microbiology↗
DOE OSTI2020

How Bulk Sensitive is Hard X-ray Photoelectron Spectroscopy: Accounting for the Cathode–Electrolyte Interface when Addressing Oxygen Redox

Sensitivity to the `bulk' oxygen core orbital makes hard X-ray photoelectron spectroscopy (HAXPES) an appealing technique for studying oxygen redox candidates. Various studies have reported an additional O 1s peak (530-531 eV) at high voltages, which has been considered a direct signature of the bulk oxygen redox process. Here, we find the emergence of a 530.4 eV O 1s HAXPES peak for three model cathodes, Li 2 MnO 3 , Li-rich NMC, and NMC 442, that shows no clear link to oxygen redox. Instead, the 530.4 eV peak for these three systems is attributed to transition metal reduction and electrolyte decomposition in the near-surface region. Claims of oxygen redox relying on photoelectron spectroscopy must explicitly account for the surface sensitivity of this technique and the extent of the cathode degradation layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Degassing fluxes in a temperate hydropower reservoir predictable by deep‐water dissolved oxygen but highly sensitive to discharge variability

Hydropower reservoirs contribute to methane (CH 4 ) and carbon dioxide (CO 2 ) emissions, like all aquatic ecosystems. Unique to hydropower reservoirs are degassing emissions that occur when deep-water intakes move water with high CH 4 and CO 2 concentrations through turbines, leading to the release of these gases. However, few studies from hydropower reservoirs have measured seasonal variability and drivers of degassing fluxes, especially in temperate systems. We measured monthly degassing emissions in temperate Douglas Reservoir (Tennessee, USA) from 2023 to 2024. We found that degassing fluxes were highest in the summertime, and deep-water CH 4 and CO 2 concentrations were predictable by deep-water dissolved oxygen (DO) concentrations. Degassing emissions accounted for 37–62% of annually estimated CH 4 emissions, outweighing ebullitive emissions during summer months. We highlight the value of using DO data to estimate deep-water CH 4 and CO 2 concentrations and degassing fluxes at higher temporal resolution to improve annualization and extrapolation of reservoir degassing emissions at broader scales.

Pilla, Rachel M. [Oak Ridge National Laboratory (O↗
DOE OSTI2021

Evaluation of Oxygen Consumption as a Sensitive Measure of Electrical Cable Polymer Insulation Degradation

Polymers used as dielectric materials in nuclear grade electrical cables, such as cross-linked polyethylene (XLPE) and ethylene-propylene rubber (EPR), are long-lived and durable. Estimating the decades-long useful service life of polymers experimentally in a feasible timeframe of weeks or months requires greatly accelerated aging in the laboratory at elevated temperatures and/or gamma dose rates. Many limitations of accelerated aging, such as due to artefacts of the process including diffusion limited oxidation and dose rate effects, have been identified that can make accurate lifetime prediction at service conditions challenging. This can be due to differences in degradation mechanisms between rapid and extended aging or to the presence of induction periods during which early aging is undetectable using common metrics of polymer insulation characterization such as tensile elongation at break. Conceptually, an ideal measure of aging would track clearly and predictably with material changes throughout the lifecycle of the evolving material state from early aging through end of useful life. With such a metric accelerated aging could be performed at much milder conditions, conditions closer to those found in long term service, and end of life calculated from the early data. Oxygen consumption has previously been proposed as a sensitive measure of insulation polymer oxidation that might meet such desirable characteristics. In this work, nuclear cable insulation samples of the two most common types, XLPE and EPR, from two of the most sourced manufacturers, RSCC and The Okonite Company, were subjected to gamma irradiation at dose rates of 100, 200, and 300 Gy/hr for up to 42 days at 26°C. The aged samples were used to evaluate oxygen consumption as a sensitive measure of aging for these materials and these conditions. For comparison and validation, the aged samples were also characterized using the more conventional tests of mass change, density, carbonyl index, and yellowness index. For both materials, oxygen consumption during irradiation was found to track consistently with applied dose—oxygen consumption rate was linear with time. Mass change and carbonyl index were also clearly proportional to exposure dose. Yellowness index, a surface sensitive measure, was observed to increase linearly with dose at low exposure levels before plateauing. Sample density was not observed to change under the conditions explored. Oxygen consumption was found to be a particularly sensitive metric to measure the degradation of polymeric cable insulation exposed to radiation. Oxygen consumption was compared to Arrhenius and time-temperature-superposition methods for activation energy calculation using literature date and found to be a useful and viable alternative for lifetime prediction. The techniques developed in this work are anticipated to be valuable in the estimation of insulation aging rates under mild conditions approaching service conditions. Direction comparison of useful life prediction by oxygen consumption with prediction via Arrhenius methodology for thermal aging and existing methods for radiation and combined thermal/radiation aging would serve to further validate this promising approach and refine our understanding of material-specific aging rates.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High Temperature Mechanical Behavior of Refractory Alloys with Digital Image Correlation

Gas turbine efficiency is typically limited by the maximum allowable temperature for components at the inlet side and in the hot gas flow. Refractory alloys and SiC/SiC ceramic-matrix composites (CMCs) are promising candidates for advancing operating temperatures beyond those of Ni-based alloys (>1200 °C). Refractory alloys are more suitable than SiC/SiC CMCs for dynamic components, due to the latter's low toughness and ductility. However, it is well known that refractory alloys suffer from poor oxidation behavior under service lifetimes and conditions, leading to embrittlement concerns. The ARPA-E ULTIMATE program has set out to combine new alloys with advanced coatings to mitigate oxidation/embrittlement effects, while increasing the mechanical performance benefits of refractory materials. Low oxygen (inert gas) or vacuum systems are needed to assess high temperature mechanical performance of developed alloys. To investigate the environmental sensitivity of candidate alloys and develop high temperature testing capabilities, four argon tensile frames were upgraded as well as a single vacuum system at Oak Ridge National Laboratory. Digital image correlation was incorporated into the vacuum frame allowing for surface strain determination and refined insight into thermomechanical response. Creep testing was performed at 1300 °C on two alloys, C-103 and MHC in vacuum and high purity argon environments. The Mo-based alloy showed less sensitivity to oxygen, indicating that testing in well-controlled argon environments may be suitable. The C-103 alloy demonstrated a stronger sensitivity to oxygen in the well-controlled argon environment, illustrating the need for the developed vacuum testing capabilities. “Small” 25 mm and “large” 76 mm MHC specimens showed comparable results in terms of strain rate during creep testing and ultimate tensile strength during tensile testing, suggesting the viability of smaller geometries that use less material of advanced developmental alloys.

Bell, Sam↗