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At least 1,099 records · Page 61

Microstructural and phase changes in alpha uranium investigated via in-situ studies and molecular dynamics

A deeper knowledge of thermally induced microstructural and phase evolution in nuclear metallic fuel can be obtained using novel in-situ microscopic analyses. Such studies can provide information on the dynamics of phase transitions which is not possible with conventional postmortem characterization (post-irradiation examination). In this work, the behavior of alpha uranium (α-U) was investigated via in-situ heating tests in a transmission electron microscope. Here, the main objective is to understand the microstructural and phase changes, such as defect annihilation and ß phase formation and retention, observed in reactor in-pile transient studies at the Transient Reactor Test facility. Indeed, defect migration and rearrangement were observed within the α phase starting at 673 K; α→ß phase transition was observed between 773 K and 1,073 K during the heating ramp (which is in the temperature window reported for α→ß transition temperatures). Recrystallization and formation of nano grains was observed at high temperatures (over 1,073 K). Such recrystallization was possibly related to the formation of the γ phase. Finally, it was indeed observed that the ß phase (but not γ phase) was retained at room temperature upon rapid cooling. Molecular dynamics studies support these experimental results and shows that the γ phase of pure uranium cannot be retained at room temperature if not stabilized with the addition of an alloying element.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Surface Energy Modulated Self‐Assembly of Percolative Gallium Nanodroplet Films for Stretchable Electronics

Advancements in soft robotics and wearable technologies have led to an increased need for flexible and stretchable electronic systems. Liquid metals like Gallium (Ga) and its alloys offer high potential in the field of stretchable electronics and photonics due to their inherent high conductivity and malleability. However, their high surface tension and native oxide formation hinder uniform wetting and continuous film formation to get conducting films. Here, we report a fabrication strategy to realize electrically conductive Ga thin films with effective thicknesses around 100 nm on polymeric and elastomeric substrates. By enhancing the surface energy of the elastomer, we create uniform Ga nanodroplets capable of sustaining stretchability up to 200% strain. Our devices exhibit electronic conduction primarily through tunneling and display strain tunable piezoresistive characteristics, which are explained using Kirchhoff's resistive network and Simmon's analytical tunneling current model. To showcase the device's capability in fields of stretchable electronics, we demonstrate several functional prototypes, including flexible devices integrated with Light Emitting Diodes (LEDs), curvature and pressure sensors, and soft robotic grippers capable of sensing object curvature. The demonstrated devices highlight the potential of this approach for scalable integration of stretchable electronics in soft robotic and wearable platforms.

42 ENGINEERING↗

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗

Ammonia eurefstics: Electrolytes for liquid energy storage and conversion at room temperature and ambient pressure

Herein we report the transformation of gaseous ammonia to a liquid at room temperature and ambient pressure through mixing with simple solid ammonium salts. The resulting liquids, named eurefstics, are potentially advantageous for the storage and electrochemical conversion of ammonia and the realization of a green ammonia energy economy. Physical properties of these eurefstics, including the temperature-dependent composition and composition-dependent densities, are reported to glean initial insight into the formation and behavior of this intriguing liquid. Preliminary electrochemical investigations of the eurefstics were also performed. We have found that these eurefstics formed are conductive and can be used directly as electrolytes for ammonia electrolysis reactions to produce hydrogen on demand. Open-circuit potential measurements were also made to determine the formal potential of the hydrogen evolution and corresponding overpotentials. Finally, safety concerns of the eurefstics are discussed in comparison with other liquid phase energy carriers.

25 ENERGY STORAGE↗

Why Are 5-Thioglycopyranosyl Donors More Axially Selective than their Glycopyranosyl Counterparts? A Low and Variable Temperature NMR Spectroscopy and Computational Study

5-Thioglycopyranosyl donors differ in reactivity and selectivity from simple glycopyranosyl donors. An extensive study has been conducted on the nature and stability of the reactive intermediates generated on the activation of per-O-acetyl and per-O-methyl 5-thioglucopyranosyl donors and the corresponding glucopyranosyl donors. Variable temperature nuclear magnetic resonance (NMR) studies with per-O-methylated or per-O-acetyl glycosyl sulfoxides and trichloroacetimidates on activation with trifluoromethanesulfonic anhydride or trimethylsilyl triflate are reported. These show that following initial adduct formation with the promoter conversion of the 5-thioglucopyranosyl donors to the 5-thioglucopyranosyl triflates requires higher temperatures than that of the glucopyranosyl donors to the glucopyranosyl triflates. It is demonstrated that neighboring group participation is a less important phenomenon for the peracetylated thioglucosyl donors than for the peracetylated glucosyl donors. A simple thiocarbenium ion was generated by protonation of 2,3-dihydro-4H-thiopyran at low temperature and characterized by NMR spectroscopy. However, the corresponding 5-thioglucopyranosyl thenium ions were not observed in any of the NMR studies of the 5-thiopyranosyl donors: the electron-withdrawing C–O bonds around the thiopyranoside core discourage thiocarbenium ion formation, just as they discourage oxocarbenium ion formation. Density functional theory (DFT) calculations reveal the tetrahydrothiopyranyl thiocarbenium ion to be approximately 2.5 kcal/mol lower in energy than the corresponding tetrahydropyranyl oxocarbenium ion relative to the corresponding covalent triflates. However, the computations reveal a 5.8 kcal/mol activation barrier for conversion of the tetrahydrothiopyranyl triflate to the thiocarbenium ion, while formation of the oxocarbenium ion–triflate ion pair from tetrahydropyranyl triflate requires only 2.6 kcal·mol –1 . Overall, the greater axial selectivity of 5-thioglycopyranosyl donors compared to analogous glycopyranosyl donors derives from (i) the lower kinetic reactivity necessitating higher reaction temperatures, (ii) the greater stability of the thiocarbenium ion over the oxocarbenium ion facilitating equilibration under thermodynamic conditions, (iii) the greater magnitude of the anomeric effect in the 5-thiosugars, and (iv) decreased neighboring group participation in the per-esterified 5-thiosugars.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double-Bilayer polar nanoregions and Mn antisites in (Ca, Sr)3Mn2O7

Abstract The layered perovskite Ca 3 Mn 2 O 7 (CMO) is a hybrid improper ferroelectric candidate proposed for room temperature multiferroicity, which also displays negative thermal expansion behavior due to a competition between coexisting polar and nonpolar phases. However, little is known about the atomic-scale structure of the polar/nonpolar phase coexistence or the underlying physics of its formation and transition. In this work, we report the direct observation of double bilayer polar nanoregions (db-PNRs) in Ca 2.9 Sr 0.1 Mn 2 O 7 using aberration-corrected scanning transmission electron microscopy (S/TEM). In-situ TEM heating experiments show that the db-PNRs can exist up to 650 °C. Electron energy loss spectroscopy (EELS) studies coupled with first-principles calculations demonstrate that the stabilization mechanism of the db-PNRs is directly related to an Mn oxidation state change (from 4+ to 2+), which is linked to the presence of Mn antisite defects. These findings open the door to manipulating phase coexistence and achieving exotic properties in hybrid improper ferroelectric.

36 MATERIALS SCIENCE↗

High-throughput investigation of crystal-to-glass transformation of Ti–Ni–Cu ternary alloy

A high-throughput investigation of metallic glass formation via solid-state reaction was reported in this paper. Combinatorial multilayered thin-film chips covering the entire Ti-Ni-Cu ternary system were prepared using ion beam sputtering technique. Microbeam synchrotron X-ray diffraction (XRD) and X-ray fluorescence (XRF) measurements were conducted, with 1,325 data points collected from each chip, to map out the composition and the phase constitution before and after annealing at 373 K for 110 hours. The composition dependence of the crystal-to-glass transition by solid-state reaction was surveyed using this approach. The resulting composition-phase map is consistent with previously reported results. Time-of-flight secondary ion mass spectroscopy (ToF-SIMS) was performed on the representative compositions to determine the inter-diffusion between layers, the result shows that the diffusion of Ti is the key factor for the crystal-to-glass transition. In addition, both layer thickness and layer sequence play important roles as well. This work demonstrates that combinatorial chip technique is an efficient way for systematic and rapid study of crystal-to-glass transition for multi-component alloy systems.

36 MATERIALS SCIENCE↗

Layer-by-layer growth of graphene oxide multilayers using robust interlayer linking chemistry. 1. Zr-bisphosphates

Graphene oxide (GO) holds substantial interest because of its utility in applications ranging from chemical sensing to catalysis and energy storage. We report on the layer-by-layer formation of graphene oxide phosphate (P-GO) multilayers on silica and oxidized silicon supports, with the layers connected via Zr-bisphosphate (ZP) linking chemistry. Layers were grown either directly by ZP linkages between P-GO sheets, or with the use of 1,4-phenylene bisphosphate (BP1) or [1,1′-biphenyl]4,4′-diyl bisphosphate (BP2). The layers have been characterized using optical null ellipsometry, X-ray photoelectron spectroscopy (XPS), UV-visible absorption spectroscopy and scanning electron microscopy (SEM). There is a linear dependence of assembly thickness on the number of layers deposited and the integrated area of the optical absorbance bands also increases linearly with number of layers deposited. XPS data provides information on interlayer linking stoichiometry. SEM images provide insight into the morphology of the adlayers, suggesting the structure and length of the interlayer linking moieties used in the multilayer assembly play a significant role in the organization of the resulting system.

Mukherjee, Neelanjana [Michigan State University, ↗

The DYRKP1 kinase regulates cell wall degradation in Chlamydomonas by inducing matrix metalloproteinase expression

Abstract The cell wall of plants and algae is an important cell structure that protects cells from changes in the external physical and chemical environment. This extracellular matrix, composed of polysaccharides and glycoproteins, must be constantly remodeled throughout the life cycle. However, compared to matrix polysaccharides, little is known about the mechanisms regulating the formation and degradation of matrix glycoproteins. We report here that a plant kinase belonging to the dual-specificity tyrosine phosphorylation-regulated kinase (DYRKP1) family present in all eukaryotes regulates cell wall degradation after mitosis of Chlamydomonas reinhardtii by inducing the expression of matrix metalloproteinases. Without DYRKP1, daughter cells cannot disassemble parental cell walls and remain trapped inside for more than 10 days. On the other hand, the dual-specificity tyrosine phosphorylation-regulated kinase complementation lines show normal degradation of the parental cell wall. Transcriptomic and proteomic analyses indicate a marked downregulation of MMP gene expression and accumulation, respectively, in the dyrkp1 mutants. The mutants deficient in matrix metalloproteinases retain palmelloid structures for a longer time than the background strain, like dyrkp1 mutants. Our findings show that dual-specificity tyrosine phosphorylation-regulated kinase, by ensuring timely MMP expression, enables the successful execution of the cell cycle. Altogether, this study provides insight into the life cycle regulation in plants and algae.

Kim, Minjae (ORCID:0000000223561295)↗

Charge density fluctuations with enhanced superconductivity at the proposed quantum critical point of Sr0.77⁢Ba0.23⁢Ni2⁢As2

A quantum critical point (QCP) represents a continuous phase transition at absolute zero. In unconventional superconductors, enhanced superconducting transition temperature and magnetic fluctuation strength are often observed together, indicating magnetism-mediated superconductivity. This raises the question of whether quantum fluctuations in other degrees of freedom, such as charge, could similarly boost superconductivity. However, because charge is frequently intertwined with magnetism, isolating and understanding its specific role in Cooper pair formation pose a significant challenge. Here, we report persistent charge density fluctuations (CDFs) down to 15 K in the nonmagnetic superconductor Sr0.77⁢Ba0.23⁢Ni2⁢As2, which lie near a proposed nematic QCP associated with a sixfold enhancement of superconductivity. Our results show that the quasielastic CDFs do not condense into resolution-limited Bragg peaks but, rather, display nonsaturated strength. The phonons associated with CDFs completely soften at 25 K, with their critical behavior described by the same mathematical framework as the antiferromagnetic Fermi liquid model, yielding a fitted Curie-Weiss temperature of 𝜃≈0K. Additionally, we find that the nematic fluctuations are weakly coupled to the lattice, as evidenced by the absence of softening in nematic-coupled in-plane transverse acoustic phonons. Our discovery positions Sr𝑥⁢Ba1−𝑥⁢Ni2⁢As2 as a promising candidate for charge-fluctuation-driven superconductivity.

Aczel, Adam [ORNL] (ORCID:0000000319641943)↗

Utah FORGE: Well 16B(78)-32 Distributed Temperature Sensing Data from April and May 2024

This dataset includes Neubrex Energy Services fiber optic distributed temperature sensing (DTS) data from well 16B(78)-32 during stimulation and circulation, including interaction with well 16A(78)-32, during April and May 2024. The DTS data are stored in HDF5 file format and are accompanied by a PowerPoint report on the study. All times in this dataset are in UTC. Depths are in MD relative to Kelly Bushing Height, and temperatures are in degrees Fahrenheit. All DTS measurements were made using a Yokogawa 3000DTSX Distributed Temperature Sensing Interrogator Unit, with a spatial sampling interval of 3.28 feet and a temporal sampling rate of 129 seconds. The third-party Pressure-Temperature Gauge data should be used with caution after April 20, 2024, as its performance is not considered reliable beyond this date.

15 GEOTHERMAL ENERGY↗

Enhancing Site Screening for Underground Hydrogen Storage: Qualitative Site Quality Assessment - SHASTA: Subsurface Hydrogen Assessment, Storage, and Technology Acceleration Project

The global shift towards renewable energy sources to mitigate fossil fuel dependency and meet carbon emission targets by 2050 has underscored the importance of innovative solutions to address energy supply-demand imbalances. Underground Hydrogen Storage (UHS) has emerged as a promising strategy to store excess renewable energy in subsurface formations for future retrieval and utilization. This report focuses on enhancing the site screening process for UHS facilities. By drawing on insights from prior research to identify key criteria influencing site suitability, our objective is to present a comprehensive set of sixteen specific criteria essential for refining the selection of UHS sites. These criteria cover various aspects such as reservoir performance, legal access, regulatory compliance, economic viability, public acceptance, and safety and security considerations. Our proposed methodology allows users to evaluate potential sites using binary responses, transitioning from isolated factors to broader considerations that facilitate a qualitative assessment of site suitability. This method enables comparative analysis and informed decision-making, supporting stakeholders in the site selection process. Our approach is designed as a guiding framework rather than a rigid template for site screening, emphasizing the importance of customizing approaches to individual circumstances. As UHS site development project evolves, adopting a comprehensive selection methodology that integrates holistic evaluations will be essential for ensuring efficient and effective site screening processes tailored to specific project needs.

08 HYDROGEN↗

Enhancing Site Screening for Underground Hydrogen Storage: Qualitative Site Quality Assessment - SHASTA: Subsurface Hydrogen Assessment, Storage, and Technology Acceleration Project

The global shift towards renewable energy sources to mitigate fossil fuel dependency and meet carbon emission targets by 2050 has underscored the importance of innovative solutions to address energy supply-demand imbalances. Underground Hydrogen Storage (UHS) has emerged as a promising strategy to store excess renewable energy in subsurface formations for future retrieval and utilization. This report focuses on enhancing the site screening process for UHS facilities. By drawing on insights from prior research to identify key criteria influencing site suitability, our objective is to present a comprehensive set of sixteen specific criteria essential for refining the selection of UHS sites. These criteria cover various aspects such as reservoir performance, legal access, regulatory compliance, economic viability, public acceptance, and safety and security considerations. Our proposed methodology allows users to evaluate potential sites using binary responses, transitioning from isolated factors to broader considerations that facilitate a qualitative assessment of site suitability. This method enables comparative analysis and informed decision-making, supporting stakeholders in the site selection process. Our approach is designed as a guiding framework rather than a rigid template for site screening, emphasizing the importance of customizing approaches to individual circumstances. As UHS site development project evolves, adopting a comprehensive selection methodology that integrates holistic evaluations will be essential for ensuring efficient and effective site screening processes tailored to specific project needs.

08 HYDROGEN↗

Self-Assembling Metabolon Enables the Cell Free Conversion of Glycerol to 1,3-Propanediol

Cell free biocatalysis is showing promise as a replacement or complement to conventional microbial biocatalysts due to the potential for achieving high yields, titers, and productivities. However, there exist several challenges that need to be addressed before its broader industrial adoption is achieved. New paradigms and innovative solutions are needed to overcome these challenges. In this study we demonstrate high levels of glycerol conversion to 1,3-propanediol using a self-assembling metabolic pathway leveraging the arraying strategy (protein scaffolds) used by thermophilic cellulolytic bacteria to assemble their biomass degrading enzymes. These synthetic metabolons were capable of producing 1,3-PDO at a yield more than 95% at lower glycerol concentration and close to 70% at higher concentrations at a higher productivity rate than the equivalent microbial strain. One of the benefits of our approach is the fact that no enzyme purification is required, and that the assembly of the complex is accomplished in vivo before immobilization, while product formation is conducted in vitro. We also report the recovery of enzymatic activity upon fusion enzymes binding to these protein scaffolds, which could have broader applications when assembling arrayed protein complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure-Induced Exciton Formation and Superconductivity in Platinum-Based Mineral Sperrylite

We report a comprehensive study of Sperrylite (PtAs 2 ), the main platinum source in natural minerals, as a function of applied pressures up to 150 GPa. While no structural phase transition is detected from pressure-dependent X-ray measurements, the unit cell volume shrinks monotonically with pressure following the third-order Birch–Murnaghan equation of state. The mildly semiconducting behavior found in pure synthesized crystals at ambient pressures becomes more insulating upon increasing the applied pressure before metalizing at higher pressures, giving way to the appearance of an abrupt decrease in resistance near 3 K at pressures above 92 GPa consistent with the onset of a superconducing phase. The pressure evolution of the calculated electronic band structure reveals the same physical trend as our transport measurements, with a non-monotonic evolution explained by a hole band that is pushed below the Fermi energy and an electron band that approaches it as a function of pressure, both reaching a touching point suggestive of an excitonic state. A Lifshitz transition of the electronic structure and an increase in the density of states may naturally explain the onset of superconductivity in this material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Combining Astrometry and Elemental Abundances: The Case of the Candidate Pre-Gaia Halo Moving Groups G03-37, G18-39, and G21-22

While most moving groups are young and nearby, a small number have been identified in the Galactic halo. Understanding the origin and evolution of these groups is an important piece of reconstructing the formation history of the halo. Here we report on our analysis of three putative halo moving groups: G03-37, G18-39, and G21-22. Based on Gaia EDR3 data, the stars associated with each group show some scatter in velocity (e.g., Toomre diagram) and integrals of motion (energy, angular momentum) spaces, counter to expectations of moving-group stars. We choose the best candidate of the three groups, G21-22, for follow-up chemical analysis based on high-resolution spectroscopy of six presumptive members. Using a new Python code that uses a Bayesian method to self-consistently propagate uncertainties from stellar atmosphere solutions in calculating individual abundances and spectral synthesis, we derive the abundances of α- (Mg, Si, Ca, Ti), Fe-peak (Cr, Sc, Mn, Fe, Ni), odd-Z (Na, Al, V), and neutron-capture (Ba, Eu) elements for each star. We find that the G21-22 stars are not chemically homogeneous. Based on the kinematic analysis for all three groups and the chemical analysis for G21-22, we conclude the three are not genuine moving groups. The case for G21-22 demonstrates the benefit of combining kinematic and chemical information in identifying conatal populations when either alone may be insufficient. Comparing the integrals of motion and velocities of the six G21-22 stars with those of known structures in the halo, we tentatively associate them with the Gaia-Enceladus accretion event.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

AEROICESTUDY Colorado State University Continuous Flow Diffusion Chamber (CFDC) version R0

This dataset comprises measurements of atmospheric ice nucleating particle (INP) number concentrations at ARM's Southern Great Plains (SGP) Site Guest Instrument Facility (GIF), in Lamont, Oklahoma, during the 2019 Aerosol-Ice Formation Closure Pilot Study (AEROICESTUDY). The results reported here are from the Colorado State University Continuous Flow Diffusion Chamber (CFDC-1H) and represent real-time measurements of ambient INPs.

54 ENVIRONMENTAL SCIENCES↗