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At least 127 records · Page 7

Analysis of the thermodynamic stability of ThO 2 and UO 2 surfaces in the presence of surfactant ligands

Nanocrystals (NCs) with size and shape dependent properties are a thriving research field. Remarkable progress has been made in the controlled synthesis of NCs of stable elements in the past two decades; however, the knowledge of the NCs of actinide compounds has been considerably limited due the difficulties in handling them both experimentally and theoretically. Actinide compounds, especially actinide oxides, play a critical role in many stages of the nuclear fuel cycle. Recently, a non-aqueous surfactant assisted approach has been developed for the synthesis of actinide oxide NCs with different morphologies, but an understanding of its control factors is still missing to date. Herein we present a comprehensive study on the low index surfaces of thorium dioxide (ThO 2 ) and their interactions with relevant surfactant ligands using density functional calculations. A systematic picture on the thermodynamic stability of ThO 2 NCs of different sizes and shapes is obtained employing empirical models based on the calculated surface energies. It is found that bare ThO 2 NCs prefer the octahedral shape terminated by (111) surfaces. Oleic acid displays selective adsorption on the (110) surface, leading to the shape transformation from octahedrons to nanorods. Other ligands such as acetylacetone, oleylamine, and trioctylphosphine oxide do not modify the equilibrium shape of ThO 2 NCs. This work provides atomic level insights into the anisotropic growth of ThO 2 NCs that was recently observed in experiments, and thus may contribute to the controlled synthesis of actinide oxide NCs with well-defined size and shape for future applications.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Red-Ox Robust SOFC Stacks for Affordable, Reliable Distributed Generation Power Systems

While SOFC systems are expected to operate reliably and with limited degradation in steady state or transient performance, SOFC stacks may ultimately fail due to the loss of structural integrity of one or several of the cells as a result of the weakening of the materials and interfaces due to physico-chemical changes that occur during continuous operation as a result of plastic and creep deformations, modification of the temperature profile, and/or degradation of the electrochemical performance of the cells. Degradation mechanisms originating from the cell components include coarsening of the microstructure over time; decomposition of materials; chemical reaction of electrode materials with electrolyte at the interface; delamination from each other; and for the anode, coking and sulfur poisoning. Of all the reliability issues that may occur for SOFCs, the main limitation for Ni-based cermet anodes (e.g., NiO-YSZ) is the poor stability during reduction-oxidation (red-ox) cycling. This project was aimed at the development of ceramic anode SOFCs based on SFCM (SrFe0.2Co0.4Mo0.4O3), which is a conductive perovskite that is red-ox stable. Additionally, the project involved the development of a red-ox robust stack. Scale up of SFCM-based cells to a large format (10 cm by 10 cm) cell size was achieved as well as a maximum power density of 0.9 W/cm 2 at 600 °C (>0.6 W/cm 2 at 0.6 V). Up to a 10-cell stack was successfully assembled and demonstrated, and cells showed similar performance in reformed, pipeline natural gas as in hydrogen. Finally, a 3-cell stack was red-ox cycled without degradation for 40 cycles at ~600 °C.

03 NATURAL GAS↗

Are sulfur isotope ratios sufficient to determine the antiquity of sulfate reduction

Possible limitations on the use of sulfur isotope ratios in sedimentary sulfides to infer the evolution of microbial sulfate reduction are discussed. Current knowledge of the ways in which stable sulfur isotope ratios are altered by chemical and biological processes is examined, with attention given to the marine sulfur cycle involving various microbial populations, and sulfur reduction processes, and it is noted that satisfactory explanations of sulfur isotope ratios observed in live organisms and in sediments are not yet available. It is furthermore pointed out that all members of the same genus of sulfate reducing bacteria do not always fractionate sulfur to the same extent, that the extent of sulfur fractionation by many sulfate-reducing organisms has not yet been determined, and that inorganic processes can also affect sulfur isotope fractionation values. The information currently available is thus concluded to be insufficient to determine the time of initial appearance of biological sulfate reduction.

Ashendorf, D.↗

Design, fabrication, and performance of foil journal bearing for the brayton rotating unit

Foil bearings were designed and manufactured to replace pivoted-shoe journal bearings in an existing Brayton Cycle turbo-alternator-compressor. The design of this unconventional rotor support was accomplished within the constraints and space limitations imposed by the present machine, and the substitution of foil bearings was effected without changes or modification other machine components. A housing and a test rig were constructed to incorporate the new foil-bearing support into a unified assemble with an air-driven rotor and the gimbal-mounted thrust bearing, seals, and shrouds of an actual Brayton Rotating Unit. The foil bearing required no external pressure source, and stable self-acting rotation was achieved at all speeds up to 43,200 rpm. Excellent wipe-wear characteristics of the foil bearing permitted well over 1000 start-stop cycles with no deterioriation of performance in the entire speed range.

Licht, L.↗

Pair-density transitions in accretion disk coronae

The thermal and e(+)e(-)-pair equilibrium structure of two-temperature disk coronae above a cool (about 10 exp 6 K) disk around a black hole of 10 solar masses are investigated. Soft photons are assumed to be amply supplied from the cool disk. Two-pair thermal equilibrium points are found for a given proton column density: the low state with very small pair density and the high state dominated by pairs. Both states are thermally unstable, while for perturbations in pair density the high state is unstable and the low state is stable. Two possible scenarios are discussed for the fate of a two-temperature corona. When the proton optical depth is relatively small (e.g., less than 1) and the temperature of input soft photons is low (e.g., less than 10 exp 6 K), the corona will undergo a limit cycle between the high state and the low state on a time scale of milliseconds. As a consequence of Compton scattering of the soft photons, the emergent spectrum in the high state is rather flat with a big Wien bump at about 100 keV, whereas it is composed of a power-law component in the low state. Some observational consequences are briefly discussed in connection with the high-low spectral transition in Cyg X-1.

Kusunose, Masaaki↗

Scalability of Cohesive Fatigue Analyses Using Explicit Solvers

A cohesive fatigue law has been integrated into a constitutive material model compatible with an explicit finite element solver. The cohesive fatigue model response is based on engineering approximations of the endurance limit and the Goodman diagram. This approach can predict stress-life diagrams for crack initiation, the Paris law regime, and transient effects of crack initiation and stable tearing. Simplified cyclic loading is utilized so that the applied load(or displacement) corresponds to the peak load of a fatigue cycle. Loads are held constant during fatigue while damage develops with increasing solution increments. An automatically-calculated ratio of fatigue cycles per solution increment controls the rate of damage growth, ensuring that damage growth is modeled with a sufficient minimum number of increments and damage growth advances to a minimum desired extent within the explicit analysis step time. The compatibility with an explicit finite element solver enables the analysis of structures that are computationally intractable for implicit finite element solvers. Scalability studies are conducted for geometrically nonlinear problems involving fiber-reinforced composite structures that exhibit fatigue damage growth of interacting matrix cracks and delaminations

Frank A Leone↗

Enhancement‐Mode PEDOT:PSS Organic Electrochemical Transistors Using Molecular De‐Doping

Abstract Organic electrochemical transistors (OECTs) show great promise for flexible, low‐cost, and low‐voltage sensors for aqueous solutions. The majority of OECT devices are made using the polymer blend poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), in which PEDOT is intrinsically doped due to inclusion of PSS. Because of this intrinsic doping, PEDOT:PSS OECTs generally operate in depletion mode, which results in a higher power consumption and limits stability. Here, a straightforward method to de‐dope PEDOT:PSS using commercially available amine‐based molecular de‐dopants to achieve stable enhancement‐mode OECTs is presented. The enhancement‐mode OECTs show mobilities near that of pristine PEDOT:PSS (≈2 cm 2 V −1 s −1 ) with stable operation over 1000 on/off cycles. The electron and proton exchange among PEDOT, PSS, and the molecular de‐dopants are characterized to reveal the underlying chemical mechanism of the threshold voltage shift to negative voltages. Finally, the effect of the de‐doping on the microstructure of the spin‐cast PEDOT:PSS films is investigated.

Keene, Scott T.↗

Application of the unsteady vortex-lattice method to the nonlinear two-degree-of-freedom aeroelastic equations

A means of numerically simulating flutter is established by implementing a predictor-corrector algorithm to solve the equations of motion. Aerodynamic loads are provided by the unsteady vortex lattice method (UVLM). This method is illustrated via the obtainment of stable and unstable responses to initial disturbances in the case of two-degree-of-freedom motion. It was found that for some angles of attack and dynamic pressure, the initial disturbance decays, for others it grows (flutter). When flutter occurs, the solution yields the amplitude and period of the resulting limit cycle. The preliminaray results attest to the feasibility of this method for studying flutter in cases that would be difficult to treat using a classical approach.

Strganac, T. W.↗

Interfacial solvation-structure regulation for stable Li metal anode by a desolvation coating technique

Rechargeable lithium (Li) metal batteries face challenges in achieving stable cycling due to the instability of the solid electrolyte interphase (SEI). The Li-ion solvation structure and its desolvation process are crucial for the formation of a stable SEI on Li metal anodes and improving Li plating/stripping kinetics. This research introduces an interfacial desolvation coating technique to actively modulate the Li-ion solvation structure at the Li metal interface and regulate the participation of the electrolyte solvent in SEI formation. Through experimental investigations conducted using a carbonate electrolyte with limited compatibility to Li metal, the optimized desolvation coating layer, composed of 12-crown-4 ether-modified silica materials, selectively displaces strongly coordinating solvents while simultaneously enriching weakly coordinating fluorinated solvents at the Li metal/electrolyte interface. This selective desolvation and enrichment effect reduce solvent participation to SEI and thus facilitate the formation of a LiF-dominant SEI with greatly reduced organic species on the Li metal surface, as conclusively verified through various characterization techniques including XPS, quantitative NMR, operando NMR, cryo-TEM, EELS, and EDS. The interfacial desolvation coating technique enables excellent rate cycling stability (i.e., 1C) of the Li metal anode and prolonged cycling life of the Li||LiCoO 2 pouch cell in the conventional carbonate electrolyte (E/C 2.6 g/Ah), with 80% capacity retention after 333 cycles.

42 ENGINEERING↗

Enhanced Performance of Silicon Anodes through Hybrid Surface Engineering

Silicon (Si) is a promising anode material for nextgeneration lithium-ion batteries (LIBs) due to its high theoretical capacity. However, Si-containing anodes typically suffer from unacceptably short lives because of the unrestricted growth of the solid electrolyte interphase (SEI). Here, in this study, hybrid surface coatings are developed to stabilize the SEI in high loading pure Si anodes using atomic and molecular layer deposition. The coatings, consisting of LiF paired with lithicone, create an ionically conductive surface that enhances the capacity retention, rate performance, and longevity. Careful binder selection helps demonstrate the full utility of the coatings by enabling high loading electrodes to cycle continuously at current densities of 1200 mA/g Si . Uncoated controls, in comparison, fail within just 10 cycles at lower loadings. X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy are used to provide supporting evidence of the coating composition and efficacy. The data indicate that our lithicone coating is converted to Li 2 CO 3 upon cycling contributing to favorable LiF/Li 2 CO 3 interfaces that enhance the space-charge effect at the active material’s surface. When applied to electrodes made with thermally stable binders and increasingly higher loadings (approaching 5 mAh/cm 2 ), ion transport through the bulk electrode, rather than SEI growth, is shown to be the limiting factor. Furthermore, data suggests a favorable interaction between lithicone precursors and poly(acrylic acid) binders mitigates thermal decomposition at higher temperatures. The work presented here represents the successful realization of composite coatings containing LiF/Li 2 CO 3 components to stabilize high-loading Si anodes. This work helps inform advanced surface engineering strategies to achieve highly reversible, high-capacity Si anodes capable of fast charging for high-performance LIBs.

atomic layer deposition↗

Ultrathin stable Ohmic contacts for high-temperature operation of β -Ga2O3 devices

Beta gallium oxide (β-Ga2O3) shows significant promise in high-temperature, high-power, and sensing electronics applications. However, long-term stable metallization layers for Ohmic contacts at high temperatures present unique thermodynamic challenges. The current most common Ohmic contact design based on 20 nm of Ti has been repeatedly demonstrated to fail at even moderately elevated temperatures (300–400 °C) due to a combination of nonstoichiometric Ti/Ga2O3 interfacial reactions and kinetically favored Ti diffusion processes. Here, we demonstrate stable Ohmic contacts for Ga2O3 devices operating up to 500–600 °C using ultrathin Ti layers with a self-limiting interfacial reaction. The ultrathin Ti layer in the 5 nm Ti/100 nm Au contact stack is designed to fully oxidize while forming an Ohmic contact, thereby limiting both thermodynamic and kinetic instability. This novel contact design strategy results in an epitaxial conductive anatase titanium oxide interface layer that enables low-resistance Ohmic contacts that are stable both under long-term continuous operation (>500 h) at 600 °C in vacuum (≤10−4 Torr), as well as after repeated thermal cycling (15 times) between room temperature and 550 °C in flowing N2. This stable Ohmic contact design will accelerate the development of high-temperature devices by enabling research focus to shift toward rectifying interfaces and other interfacial layers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Cradle to grave: the importance of the fuel cycle to molten salt reactor sustainability

Advanced reactor technologies are being considered for the next-generation of nuclear power plants. These plants are designed to have a smaller footprint, run more efficiently at higher temperatures, have the flexibility to meet specific power or heating needs, and have lower construction costs. This paper offers a perspective on molten salt reactors, promoted as having a flexible fuel cycle and close-to-ambient pressure operation. A complexity introduced by reducing the reactor footprint is that it may require low-enriched fuel for efficient operation, available from enrichment of the feed salt or by reusing actinides from existing used nuclear fuel (UNF). Recycling UNF has the potential to reduce high-level waste, if done correctly. Release limits from UNF processing are stringent, and processes for waste reduction, fission gas trapping, and stable waste-form generation are not yet ready for commercial deployment. These complex processes are expensive to develop and troubleshoot because the feed is highly radioactive. Thus, fuel production and supply chain development must keep abreast of reactor technology development. Another aspect of reactor sustainability is the non-fuel waste streams that will be generated during operation and decommissioning. Some molten salt reactor designs are projected to have much shorter operational lifetimes than light-water reactors: less than a decade. A goal of the reactor sustainability effort is to divert these materials from a high-level waste repository. However, processing of reactor components should only be undertaken if it reduces waste. Economic and environmental aspects of sustainability are also important, but are not included in this perspective.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Search for Pulsations from a Nearby Millisecond Pulsar and Wasilewski 49: Mirror for a Hidden Seyfert 1 Nucleus

Five studies are reported in this final report. The recently discovered 5.3 ms pulsar J1012+5307 at a distance of 520 pc is in an area of the sky which is particularly deficient in absorbing gas. The column density along the line of sight is less than 7.5 x 10(exp 19) CM(exp -2) which facilitates soft X-ray observations. Halpern reported a possible ROSAT Position Sensitive Proportional Counter (PSPC) detection of the pulsar in a serendipitous, off-axis observation. We have now confirmed the X-ray emission of PSR J1012+,5307 in a 23 ksec observation with the ROSAT High Resolution Imager (HRI). A point source is detected within 3" of the radio position. Its count rate of 1.6 +/- 0.3 x 10(exp -3) s(exp -1) corresponds to an unabsorbed 0. 1-2.4 keV flux of 6.4 x 10(exp -14) ergs cm(exp -2) s(exp -1), similar to that reported previously. This counts-to-flux conversion is valid for N(sub H) = 5 x 10(exp 19) cm(exp -2), and either a power-law spectrum of photon index 2.5 or a blackbody of kT = 0.1 keV. The implied X-ray luminosity of 2.0 x 10(exp 30) ergs s(exp -1) is 5 X 10(exp -4) of the pulsar's spin-down power dot-E, and similar to that of the nearest millisecond pulsar J0437-4715, which is nearly a twin of J1012+5307 in P dot-E. We subjected the 37 photons (and 13 background counts) within the source region to a pulsar search, but no evidence for pulsation was found. The pulsar apparently emits over a large fraction of its rotation cycle, and the absence of sharp modulation can be taken as evidence for surface thermal emission, as is favored for PSR J0437-4715, rather than magnetospheric X-ray emission which is apparent in the sharp pulses of the much more energetic millisecond pulsar B1821-24. A further test of this interpretation will be made with a longer ROSAT observation, which will increase the number of photons collected by a factor of 5, and permit a more sensitive examination of the light curve for modulation due to emission from heated polar caps. If found, such modulation will be further evidence that surface reheating by the impact of particles accelerated along open fiel;d lines operates in these approximately 10(exp -9) year old pulsars. In a second study, a new AM Her star serendipitously in a 25 day observation was detected with the EUVE satellite. A coherent period of 85.82 min is present in the EUVE Deep Survey imager light curve of this source. A spectroscopic optical identification is made with a 19th magnitude blue star that has H and He emission lines, and broad cyclotron humps typical of a magnetic cataclysmic variable. A lower limit to the polar magnetic field of 50 MG is estimated from the spacing of the cyclotron harmonics. EUVE J0425.6-5714 is also detected in archival ROSAT HRI observations spanning two months, and its stable and highly structured light curve permits us to fit a coherent ephemeris linking the ROSAT and EUVE data over a 1.3 yr gap. The derived period is 85.82107 +/- 0.00020 min, and the ephemeris should be accurate to 0.1 cycles until the year 2005. A narrow but partial X-ray eclipse suggests that this object belongs to the group of AM Her stars whose viewing geometry is such that the accretion stream periodically occults the soft X-ray emitting accretion spot on the surface of the white dwarf. A non-detection of hard X-rays from ASCA observations that are contemporaneous with the ROSAT HRI shows that the soft X-rays must dominate by at least an order of magnitude, which is consistent with a known trend among AM Her stars with large magnetic field. This object should not be confused with the Seyfert galaxy IH 0419-577 (= LB 1727), another X-ray/EUV source which lies only 3'95 away, and was the principal target of these monitoring observations. In a third report; the identity of the persistent high-energy (> 100 MeV) gamma-ray sources in the Galaxy, still largely a mystery is investigated. The second installment of the EGRET (2EG) lists a total of 128 sources, of which 51 are likely or possibly identified with AGNs, five with rotation-powered pulsars, and one is the LMC. There are 71 unidentified sources, of which 33, or almost half, lie in the narrow band of absolute value of b < 10 degrees along the Galactic plane. This excess of low-latitude sources must, therefore, constitute a Galactic population that is either similar to the already identified gamma-ray pulsars, or an entirely new class of gamma-ray emitters associated with the disk population. We are continuing our program, begun in A06, that is aimed at intermediate-latitude sources, arguing that X-ray detection of them is the most plausible method of identifying the Galactic population. The sources at high latitude must statistically be mostly AGNS, and are more straightforwardly identified through radio and optical means. For the fourth report, identification of the EGRET Source the identity of the persistent, high-energy gamma-ray sources in the Galactic plane is a mystery. The most likely scenario is a population of middle-aged pulsars, many of which could be radio quiet like Geminga. We have an ongoing program of ROSAT, VLA, and optical observations of selected EGRET error circles at intermediate Galactic latitude. For one of these fields, at (l, b) = (106 degrees, +3), our complete census of X-ray and radio sources, reveals a remarkable association between a radio shell with unique properties, and a complete census of X-ray and radio sources reveals a remarkable association between a radio shell with unique properties, and a compact X-ray source. Further observations are needed to determine whether or not this source has a hard X-ray spectrum like that of other gamma ray pulsars and, ideally, to find its pulsations. A fifth report reviews, Wasilewski 49, an interacting pair of Seyfert galaxies at z = 0.063, one of which contains a hidden Seyfert I nucleus as evidenced by broad wings on its Balmer lines.

Halpern, Jules P.↗

Unraveling interphase-driven failure pathways in LiMn0.6Fe0.4PO4/graphite pouch cells

LiMnxFe1−xPO4 (LMFP) is a promising high-voltage, thermally stable, and earth-abundant cathode material, yet its practical application is limited by interphase instability and Mn dissolution. In this work, we systematically evaluate LiMn0.6Fe0.4PO4/graphite pouch cells using three electrolyte formulations including control carbonate electrolyte, control + 2 wt% vinylene carbonate (VC), and control + 2 wt% VC + 1 wt% 1,3,2-dioxathiolane 2,2-dioxide (DTD), to establish how electrolyte composition governs interphase chemistry and long-term degradation. Electrochemical testing shows that both additives are preferentially reduced prior to ethylene carbonate (EC) during cell formation, generating robust cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers that suppress gas evolution and raise the first-cycle coulombic efficiency to 89.3%. Additionally, the dual-additive electrolyte delivers the most stable performance, retaining over 85% capacity after 600 cycles while minimizing impedance growth under long-term cycling at C/3 and 40 °C. Soft X-ray absorption spectroscopy confirms that VC + DTD effectively suppresses electrolyte oxidation at the cathode surface, and micro-X-ray fluorescence shows substantially reduced Mn dissolution and deposition on the graphite anode. Density functional theory simulations further provided insights into the structural and energetic influences of alkoxide species on the cathode surface, proposing a Mn2+ extraction mechanism. The combined experimental and computational findings establish a mechanistic link between electrolyte composition and interphase evolution, highlighting the effectiveness of electrolyte engineering for extending the operational lifetime of LMFP-based lithium-ion batteries.

Chak, Chanmonirath Michael↗

Low-nickel cathode chemistry for sustainable and high-energy lithium-ion batteries

The transition to sustainable energy storage demands lithium-ion batteries with high energy density and reduced reliance on critical metals such as nickel (Ni), yet current strategies to increase capacity have largely depended on raising Ni content, leading to escalating supply risks, rising costs and sustainability concerns. More critically, Ni-rich cathodes suffer from rapid electrochemical degradation driven by structural instability, creating an insurmountable trade-off between capacity and cycle life. Here, in this study, we introduce a low-Ni chemistry cathode, Li(Li 0.05 Ni 0.57 Mn 0.31 Co 0.07 )O 2 , with a radial phase integration design that overcomes these limitations, enabling a remarkable Ni usage reduction (Ni < 0.6) while demonstrating high capacity (215 mAh g −1 ) and markedly improved cyclability (~97% retention over 400 cycles) compared to conventional high-Ni cathodes (Ni = 0.8). Advanced X-ray and electron microscopy analyses reveal that the designed cathode exhibits a highly reversible oxygen anionic redox, benefiting from a structurally stable surface and minimizing irreversible phase transitions. Moreover, the integrated structure substantially mitigates lattice strain and improves mechanical stability even under harsh conditions. In conclusion, this advance offers a general design principle for developing next-generation cathodes that combine resource efficiency with long-term electrochemical reliability.

36 MATERIALS SCIENCE↗

Digital second-order phase-locked loop

A digital second-order phase-locked loop is disclosed in which a counter driven by a stable clock pulse source is used to generate a reference waveform of the same frequency as an incoming waveform, and to sample the incoming waveform at zero-crossover points. The samples are converted to digital form and accumulated over M cycles, reversing the sign of every second sample. After every M cycles, the accumulated value of samples is hard limited to a value SGN = + or - 1 and multiplied by a value delta sub 1 equal to a number of n sub 1 of fractions of a cycle. An error signal is used to advance or retard the counter according to the sign of the sum by an amount equal to the sum.

Holes, J. K.↗

Cyanobacterial Biofertilizer Production by Guanidine-Producing Enzymes

Cyanobacterial production of a biofertilizer shows promise as an environmentally benign alternative to conventional nitrogen fertilizers, reducing environmental and energy burdens through light-driven nitrogen and carbon fixation. One route to realizing the potential for a nitrogen-rich, slow-releasing biofertilizer involves the genetic engineering of cyanobacteria to produce guanidine. Recent advances have demonstrated enzymatic guanidine production in cyanobacteria, but an understanding of cyanobacterial guanidine metabolism is still limited. This Perspective highlights strategies and opportunities for cyanobacterial guanidine production in a Design−Build−Test−Learn cycle. Exploring new guanidine-producing enzymes via phylogenetics could expand candidate enzymes, while understanding the metabolism of substrates can identify constraints and opportunities in substrate utilization. Additionally, guanidine sensing and export are crucial areas of study to enable continuous fertilizer production and stable nitrogen flux. These strategies will guide the development of advanced nitrogen biofertilizer strategies for the agricultural sector.

09 BIOMASS FUELS↗