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At least 379 records · Page 21

Superior zero thermal expansion dual-phase alloy via boron-migration mediated solid-state reaction

Rapid progress in modern technologies demands zero thermal expansion (ZTE) materials with multi-property profiles to withstand harsh service conditions. Thus far, the majority of documented ZTE materials have shortcomings in different aspects that limit their practical utilization. Here, we report on a superior isotropic ZTE alloy with collective properties regarding wide operating temperature windows, high strength-stiffness, and cyclic thermal stability. A boron-migration-mediated solid-state reaction (BMSR) constructs a salient “plum pudding” structure in a dual-phase Er-Fe-B alloy, where the precursor ErFe 10 phase reacts with the migrated boron and transforms into the target Er 2 Fe 14 B (pudding) and α-Fe phases (plum). The formation of such microstructure helps to eliminate apparent crystallographic texture, tailor and form isotropic ZTE, and simultaneously enhance the strength and toughness of the alloy. These findings suggest a promising design paradigm for comprehensive performance ZTE alloys.

36 MATERIALS SCIENCE↗

New Fe 59 Stellar Decay Rate with Implications for the Fe 60 Radioactivity in Massive Stars

The discrepancy between observations from γ-ray astronomy of the 60 Fe/ 26 Al γ-ray flux ratio and recent calculations is an unresolved puzzle in nuclear astrophysics. The stellar β-decay rate of 59 Fe is one of the major nuclear uncertainties impeding us from a precise prediction. The important Gamow-Teller strengths from the low-lying states in 59 Fe to the 59 Co ground state are measured for the first time using the exclusive measurement of the 59 Co(t,3He+γ) 59 Fe charge-exchange reaction. The new stellar decay rate of 59 Fe is a factor of 3.5±1.1 larger than the currently adopted rate at T=1.2 GK. Stellar evolution calculations show that the 60 Fe production yield of an 18 solar mass star is decreased significantly by 40% when using the new rate. Our result eliminates one of the major nuclear uncertainties in the predicted yield of 60 Fe and alleviates the existing discrepancy of the 60 Fe/ 26 Al ratio.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Machine Learning Design of Perovskite Catalytic Properties

Abstract Discovering new materials that efficiently catalyze the oxygen reduction and evolution reactions is critical for facilitating the widespread adoption of solid oxide fuel cell and electrolyzer (SOFC/SOEC) technologies. Here, machine learning (ML) models are developed to predict perovskite catalytic properties critical for SOFC/SOEC applications, including oxygen surface exchange, oxygen diffusivity, and area specific resistance (ASR). The models are based on trivial‐to‐calculate elemental features and are more accurate and dramatically faster than the best models based on ab initio‐derived features, potentially eliminating the need for ab initio calculations in descriptor‐based screening. The model of ASR enables temperature‐dependent predictions, has well calibrated uncertainty estimates and online accessibility. Use of temporal cross‐validation reveals the model to be effective at discovering new promising materials prior to their initial discovery, demonstrating the model can make meaningful predictions. Using the SHapley Additive ExPlanations (SHAP) approach, detailed discussion of different approaches of model featurization is provided for ML property prediction. Finally, the model is used to screen more than 19 million perovskites to develop a list of promising cheap, earth‐abundant, stable, and high performing materials, and find some top materials contain mixtures of less‐explored elements (e.g., K, Bi, Y, Ni, Cu) worth exploring in more detail.

25 ENERGY STORAGE↗

How a Formate Dehydrogenase Responds to Oxygen: Unexpected O 2 Insensitivity of an Enzyme Harboring Tungstopterin, Selenocysteine, and [4Fe–4S] Clusters

The reversible two-electron interconversion of formate and CO 2 is catalyzed by both nonmetallo- and metallo-formate dehydrogenases (FDHs). The latter group comprises molybdenum- or tungsten-containing enzymes with the metal coordinated by two equivalents of a pyranopterin cofactor, a cysteinyl or selenocysteinyl (Sec) ligand supplied by the polypeptide, and a catalytically essential terminal sulfido ligand. In addition, these biocatalysts incorporate one or more [4Fe–4S] clusters for facilitating long-distance electron transfer. However, an interesting dichotomy arises when attempting to understand how the metallo-FDHs react with O 2 . Whereas existing scholarship portrays these enzymes as being unable to perform in air due to extreme O 2 lability of their metal centers, studies dating as far back as the 1930s emphasize that some of these systems exhibit formate oxidase (FOX) activity, coupling formate oxidation to O 2 reduction. Therefore, to reconcile these conflicting views, we explored context-dependent functional linkages between metallo-FDHs and their cognate electron acceptors within the same organism vis-à-vis catalysis under atmospheric O 2 . Here, we report the discovery and characterization of an O 2 -insensitive FDH2 from the sulfate-reducing bacterium Desulfovibrio vulgaris Hildenborough (DvH) that ligates tungsten, Sec, and four [4Fe–4S] clusters. By advancing a robust expression platform for its recombinant production, we eliminate both the requirement of nitrate or azide during purification and reductive activation with thiols and/or formate prior to catalysis. Because the distinctive spectral signatures of formate-reduced DvH-FDH2 remain invariant under anaerobic and aerobic conditions, we benchmarked the enzyme activity in air, identifying CO 2 as the catalytic product. Full reaction progress curve analysis discloses a high catalytic efficiency when probed with a high-potential artificial electron acceptor. Furthermore, we show that DvH-FDH2 enables near-stoichiometric hydrogen peroxide production without superoxide release to achieve O 2 insensitivity. Notably, simultaneous electron transfer to cytochrome c and O 2 reveals that metal-based electron bifurcation is operational in this system. Taken together, our work proves the co-occurrence of redox bifurcated FDH and FOX activities within a metalloenzyme scaffold. These findings set the stage for uncovering previously unknown O 2 -insensitive flavin-based electron bifurcation mechanisms, as well as for developing authentic formate/air biofuel cells, engineering O 2 -stable FDHs and biohybrid metallocatalysts, and discerning formate bioenergetics of gut microbiota.

13C NMR↗

Metabolic flux analysis reaching genome wide coverage: lessons learned and future perspectives

13 C-MFA is currently the only technique capable of elucidating intracellular metabolic fluxes. Generally, in 13 C-MFA studies the reactions that can carry flux are mostly pre-specified by only considering canonical pathways and ignoring alternate ones. This may bias flux elucidation and cause labeling data to erroneously confirm implied assumptions. Here, by expanding the scope of the metabolic mapping models to match known genome-scale metabolism such estimation biases can be eliminated. However, this model expansion to genome-scale requires the construction of expanded atom mapping models, more efficient flux estimation algorithms, and formal estimation of confidence levels. Even though significant progress has been made in this direction, a number of challenges remain before widespread adoption by the community.

59 BASIC BIOLOGICAL SCIENCES↗

Comparative study of flux pinning flux creep and critical currents between YBaCuO crystals with and without Y2BaCuO5 inclusions

In the Y-Ba-Cu-O system YBa2Cu3Ox phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3Ox. Through the control of processing conditions and starting compositions it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and without 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

Murakami, Masato↗

Products of Dissociative Recombination in the Ionosphere

SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion source for O2(+), NO(+), and N2(+) beams. Translational spectroscopy of the products of dissociative charge transfer in Cs vapor was used to accurately assay the composition of the O2(+) and NO(+) beams and to develop a methodology for the vibrationally controlled preparation of the ground state ion beams. Attempts to assay the N2(+) beam revealed a novel two-electron process in the charge transfer reactions. A coaxial electron gun for the DR measurements was constructed following an extensive numerical design of the fields. Tests of the gun, however, found substantial perturbations of the magnetic fields by the soft iron (CMI-C) assembly containing the Langmuir probe that locates the electron beam. Hydrogen annealing of the iron failed to eliminate the field perturbations, necessitating the removal of the probe assembly. During this work on the coaxial electron gun, we discovered that predissociated high Rydberg states of O2 could be produced by subjecting the molecules to a sudden perturbation by an electromagnetic field. This technique allowed a measurement of the product branching to the atomic limits for the lowest seven vibrational levels of O2(+).

Cosby, Philip↗

Recruiting Perovskites to Degrade Toxic Trinitrotoluene

Everybody knows TNT, the most widely used explosive material and a universal measure of the destructiveness of explosions. A long history of use and extensive manufacture of toxic TNT leads to the accumulation of these materials in soil and groundwater, which is a significant concern for environmental safety and sustainability. Reliable and cost-efficient technologies for removing or detoxifying TNT from the environment are lacking. Despite the extreme urgency, this remains an outstanding challenge that often goes unnoticed. We report here that highly controlled energy release from explosive molecules can be accomplished rather easily by preparing TNT–perovskite mixtures with a tailored perovskite surface morphology at ambient conditions. These results offer new insight into understanding the sensitivity of high explosives to detonation initiation and enable many novel applications, such as new concepts in harvesting and converting chemical energy, the design of new, improved energetics with tunable characteristics, the development of powerful fuels and miniaturized detonators, and new ways for eliminating toxins from land and water.

36 MATERIALS SCIENCE↗

A Unified Approach to Decarboxylative Halogenation of (Hetero)aryl Carboxylic Acids

Aryl halides are a fundamental motif in synthetic chemistry, playing a critical role in metal-mediated cross-coupling reactions and serving as important scaffolds in drug discovery. Although thermal decarboxylative functionalization of aryl carboxylic acids has been extensively explored, the scope of existing halodecarboxylation methods remains limited, and there currently exists no unified strategy that provides access to any type of aryl halide from an aryl carboxylic acid precursor. Herein, we report a general catalytic method for direct decarboxylative halogenation of (hetero)aryl carboxylic acids via ligand-to-metal charge transfer. This strategy accommodates an exceptionally broad scope of substrates. Here, we leverage an aryl radical intermediate toward divergent functionalization pathways: (1) atom transfer to access bromo- or iodo(hetero)arenes or (2) radical capture by copper and subsequent reductive elimination to generate chloro- or fluoro(hetero)arenes. The proposed ligand-to-metal charge transfer mechanism is supported through an array of spectroscopic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Upcycling waste PET into functional multiblock copolymers through controlled macromolecular design

Poly(ethylene terephthalate) (PET) oligomers derived from glycolysis depolymerization were converted into multiblock copolymers through diisocyanate-mediated coupling with dihydroxy-terminated oligomers, enabling precise control over copolymer sequence distribution, connectivity, and mechanical performance. Here, we demonstrate that telechelic PET oligomers isolated directly from depolymerized consumer waste can serve as reactive building blocks for the formation of segmented multiblock copolymers, eliminating the need to revert to monomeric feedstocks. Dihydroxy-terminated PET oligomers (Mw ≈ 8 kg mol−1) were coupled with poly(ethylene oxide) (PEO, Mw ≈ 4 kg mol−1) to form PET-PEO multiblock copolymers with high molar mass (Mw ≈ 160 kg mol−1). We further show that the timing of end-capping reactions provides a key control parameter that governs the competition between chain extension and termination, thereby dictating the resulting multiblock architecture and molecular-weight evolution. Evaluation of their mechanical properties reveals that virgin PET exhibits high modulus (∼3 GPa) and strength (43 MPa) but limited ductility (<10% elongation). In contrast, PET–PEO multiblock copolymers retain comparable tensile strength (44 MPa), albeit while exhibiting dramatically enhanced ductility (>90% elongation), forming tougher materials with efficient stress transfer between the rigid PET domains and the flexible PEO segments. When incorporated into PET/PEO blends at low loadings, the multiblock copolymers serve as effective compatibilizers, yielding materials with an intermediate modulus (1.1–1.2 GPa) and improved elongation compared to uncompatibilized blends. Furthermore, the presence of PEO blocks increases water uptake and gas permeability relative to virgin PET, reflecting the tunability of molecular transport through the copolymeric blocks. To our knowledge, this represents the first report of PET–PEO multiblock copolymers derived from post-consumer PET for gas transport applications. These results demonstrate that multiblock copolymer formation from telechelic PET oligomers provides a versatile platform for tailoring the mechanical and transport behavior of polyester-based materials through controlled macromolecular design and establishes a generalizable strategy for transforming consumer plastic waste into functional segmented polymers without requiring complete depolymerization to monomers.

Watson-Sanders, Shelby [Department of Chemistry, U↗

Mapping structures and dynamics with frequency-correlated diffusion exchange

Understanding molecular motion in diffusion-driven complex environments is critical for designing sustainable materials and improving chemical processes. Here, we introduce a multidimensional nuclear magnetic resonance (NMR) method that captures how molecular populations exchange across different dynamic regimes. By extending the modulated gradient spin-echo technique to include frequency-frequency correlations, our approach reveals diffusion pathways that are otherwise obscured in heterogeneous systems. Implemented on a unilateral NMR magnet, the method eliminates gradient pulsing constraints and accesses dynamics in the kilohertz regime. We apply this technique to swelling and acid-catalyzed deconstruction of cross-linked and linear polymers to observe how structural heterogeneity evolves over time. By linking molecular motion to topology and chemical state, we extract physical metrics such as fractal surface dimensionality and reaction wavefront velocity, properties inaccessible with standard diffusion measurements. This work expands the capabilities of NMR for probing soft matter, with implications for polymer recycling and materials design.

Fricke, Sophia N. [University of California, Berke↗

Additive-Mixing Fuel Injection (AMFI): A device for robust control and improved performance of high-efficiency LTGC engines

Low-temperature gasoline combustion (LTGC) engines can provide high efficiencies with very low NOx and particulate emissions. Despite these major advantages, methods for controlling LTGC combustion timing, achieving robust autoignition, and good low-load performance have challenged the development of practical LTGC engines. A key reason is that the ideal reactivity of the fuel varies with operating conditions, with low-reactivity fuels working well at high loads and higher-reactivity fuels working better at low loads. This article introduces a new technique called Additive Mixing Fuel Injection (AMFI) that adjusts the reactivity of the gasoline to obtain good performance over the operating map. Moreover, AMFI can provide robust combustion-timing control because it precisely meters very small amounts (0.01–0.6 mm 3 ) of an ignition-enhancing additive into the fuel each engine cycle. The additive used was 2-ethylhexyl nitrate (EHN), a common, inexpensive diesel-fuel ignition improver, but other additives could be used. Because additive amounts are so small, a 2-gal reservoir would be sufficient for medium-duty applications with refilling only at service intervals of about 8000 mi. The AMFI system has been installed on a single-cylinder LTGC research engine and demonstrated to provide robust combustion-timing control over wide ranges of combustion phasing, fueling rate, intake boost, engine speed, and intake temperature. AMFI also increases the fuel’s reactivity sufficiently to greatly reduce or eliminate the need for charge heating, simplifying engine design and significantly increasing thermal efficiency and the maximum load at low-boost conditions. The nitrogen in the EHN produced a modest increase in NOx, but it was mitigated by lower intake temperatures, and NOx emissions remained very low. Finally, the additive increases the sensitivity of autoignition reactions to variations in the local fuel/air mixture within the charge. This allows the use of controlled fuel stratification for improved LTGC-engine performance, and its potential to improve low-load operation was demonstrated.

Dec, John E.↗

Extending the life and recycle capability of earth storable propellant systems.

Rocket propulsion systems for reusable vehicles will be required to operate reliably for a large number of missions with a minimum of maintenance and a fast turnaround. For the space shuttle reaction control system to meet these requirements, current and prior related system failures were examined for their impact on reuse and, where warranted, component design and/or system configuration changes were defined for improving system service life. It was found necessary to change the pressurization component arrangement used on many single-use applications in order to eliminate a prevalent check valve failure mode and to incorporate redundant expulsion capability in propellant tank designs to achieve the necessary system reliability. Material flaws in pressurant and propellant tanks were noted to have a significant effect on tank cycle life. Finally, maintenance considerations dictated a modularized systems approach, allowing the system to be removed from the vehicle for service and repair at a remote site.

Schweickert, T. F.↗

Comparative study of flux pinning, creep and critical currents between YBaCuO crystals with and without Y2BaCuO5 inclusions

In the Y-Ba-Cu-O system, YBa2Cu3O(x) phase is produced by the following peritectic reaction: Y2BaCuO5 + liquid yields 2YBa2Cu3O(x). Through the control of processing conditions and starting compositions, it becomes possible to fabricate large crystals containing fine Y2BaCuO5(211) inclusions. Such crystals exhibit Jc values exceeding 10000 A/sq cm at 77 K and 1T. Recently, researchers developed a novel process which can control the volume fraction of 211 inclusions. Elimination of 211 inclusions is also possible. In this study, researchers prepared YBaCuO crystals with and without 211 inclusions using the novel process, and compared flux pinning, flux creep and critical currents. Magnetic field dependence of Jc for YBaCuO crystals with and with 211 inclusions is shown. It is clear that fine 211 inclusions can contribute to flux pinning. It was also found that flux creep rate could be reduced by increasing flux pinning force. Critical current density estimates based on the conventional flux pinning theory were in good agreement with experimental results.

Murakami, Masato↗

Highly porous ceramic oxide aerogels having improved flexibility

Ceramic oxide aerogels incorporating periodically dispersed flexible linkages are provided. The flexible linkages impart greater flexibility than the native aerogels without those linkages, and have been shown to reduce or eliminate the need for supercritical CO.sub.2-mediated drying of the corresponding wet gels. The gels may also be polymer cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions.

Meador, Mary Ann B.↗

Chrome-free qandilite (Mg 2 TiO 4 ) refractory aggregates: Role of titania source and evaluation of thermal expansion coefficient

As used chrome-based refractories may contain toxic Cr 6+ , the chrome-free Mg 2 TiO 4 phase is being considered which is known to improve hot strength and resistance to thermal shock and slag corrosion. As in situ Mg 2 TiO 4 formation generates porosity, preformed aggregates are desirable. Dilatometric studies revealed that when dead burned magnesia is combined with industrial anatase instead of rutile, it expanded less (1% versus 7.2%) and the reaction occurred earlier (965°C compared to 1120°C). After sintering at 1,600°C, rutile produced an aggregate with 3.8% open porosity, whereas anatase led to 0 % porosity and a bulk density of 3.24g/cm 3 with a thermal expansion coefficient (70–1,600°C) of 13.5×10 -6 K -1 . Moreover, replacing rutile by anatase eliminates the undesirable MgTiO 3 phase. The anatase-based aggregate consisted of a Mg 2 TiO 4 matrix with residual unreacted MgO and an intergranular, refractory CaTiO 3 phase. In conclusion, the rutile-based aggregate was deemed unsuitable due to a low-melting microstructure of forsterite contiguous with CaTiO 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Edible carbohydrates from formaldehyde in a spacecraft

The autocatalytic nature of the base catalyzed condensation of formaldehyde to formose sugars is eliminated by using as a cocatalyst, an aldose, or ketose having an alpha-hydrogen. This is more strongly complexed by base than is formaldehyde and the cocatalyst and sugar products accumulate as catalyst complexes instead of formaldehyde. Because of the presence of alpha-hydrogen atoms in cocatalysts and formose sugars, their removal by cross Cannizzaro reaction of complexed sugars does not occur, so the formose reaction behaves autocatalytically due to this accumulation. It is believed that a given catalytic formose complex is not a discrete complexed sugar, but rather, a scrambled dynamic mixture of sugars having weakened structures. The sugar complexes derive from a common salt-like formaldehyde complex, which, because of the absence of alpha-hydrogen, has a greater tendency to undergo Cannizzaro reaction, rather than formose condensation. Because of this, the Cannizzaro reaction can proceed without measurable formose condensation. The reverse is not possible.

Weiss, A. H.↗

Non-Toxic Orbiter Maneuvering System (OMS) and Reaction Control System

NASA is pursuing the technology and advanced development of a non-toxic (NT) orbital maneuvering system (OMS) and reaction control system (RCS) for shuttle upgrades, RLV, and reusable first stages. The primary objectives of the shuttle upgrades program are improved safety, improved reliability, reduced operations time and cost, improved performance or capabilities, and commonality with future space exploration needs. Non-Toxic OMS/RCS offers advantages in each of these categories. A non-toxic OMS/RCS eliminates the ground hazards and the flight safety hazards of the toxic and corrosive propellants. The cost savings for ground operations are over $24M per year for 7 flights, and the savings increase with increasing flight rate up to $44M per year. The OMS/RCS serial processing time is reduced from 65 days to 13 days. The payload capability can be increased up to 5100 Ibms. The non-toxic OMS/RCS also provides improved space station reboost capability up to 20 nautical miles over the current toxic system of 14 nautical miles. A NT OMS/RCS represents a clear advancement in the SOA over MMH/NTO. Liquid oxygen and ethanol are clean burning, high-density propellants that provide a high degree of commonality with other spacecraft subsystems including life support, power, and thermal control, and with future human exploration and development of space missions. The simple and reliable pressure-fed design uses sub-cooled liquid oxygen at 250 to 350 psia, which allows a propellant to remain cryogenic for longer periods of time. The key technologies are thermal insulation and conditioning techniques are used to maintain the sub-cooling. Phase I successfully defined the system architecture, designed an integrated OMS/RCS propellant tank, analyzed the feed system, built and tested the 870 lbf RCS thrusters, and tested the 6000 lbf OMS engine. Phase 11 is currently being planned for the development and test of full-scale prototype of the system in 1999 and 2000

Hurlbert, Eric A.↗