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At least 361 records · Page 20

Tuning Interface Electronic Properties via Chiral Two‐Dimensional Metal‐Organic Frameworks

Control over structural symmetries in nanomaterials offers a powerful approach to engineer electronic properties. For instance, breaking of mirror symmetries in two-dimensional (2D) materials with a hexagonal lattice can lead to nontrivial electronic topologies and correlated-electron phenomena. Yet, the impact of structural chirality on the electronic properties of 2D materials and interfaces remains underexplored. Here, how chiral phases of a 2D metal-organic framework (MOF) with a hexagonal lattice—consisting of hexaazatriphenylene molecules coordinated to Cu atoms—scatter, confine, and perturb the Shockley surface state (SS) electrons of an underlying Ag(111) substrate is investigated. Via low-temperature scanning tunneling microscopy and spectroscopy, noncontact atomic force microscopy, and numerical calculations based on an electronic plane-wave expansion method, modifications of the Ag(111) SS band structure are shown and quantified, including gap openings and lifts of band degeneracies, driven exclusively by the structural chirality of the 2D MOF phases. These findings highlight how structural symmetries, in particular chirality, affect electronic states at material interfaces, expanding on the toolkit for designing 2D materials with tailored electronic properties.

band structure engineering↗

Search for long-lived particles produced in association with a Z boson in proton-proton collisions at $\sqrt{s}$ = 13 TeV

A search for long-lived particles (LLPs) produced in association with a Z boson is presented. The study is performed using data from proton-proton collisions with a center-of-mass energy of 13 TeV recorded by the CMS experiment during 2016–2018, corresponding to an integrated luminosity of 117 fb -1 . The LLPs are assumed to decay to a pair of standard model quarks that are identified as displaced jets within the CMS tracker system. Triggers and selections based on Z boson decays to electron or muon pairs improve the sensitivity to light LLPs (down to 15 GeV). This search provides sensitivity to beyond the standard model scenarios which predict LLPs produced in association with a Z boson. In particular, the results are interpreted in the context of exotic decays of the Higgs boson to a pair of scalar LLPs (H → SS). The Higgs boson decay branching fraction is constrained to values less than 6% for proper decay lengths of 10–100 mm and for LLP masses between 40 and 55 GeV. In the case of low-mass (≈ 15 GeV) scalar particles that subsequently decay to a pair of b quarks, the search is sensitive to branching fractions B(H → SS) < 20% for proper decay lengths of 10–50 mm. The use of associated production with a Z boson increases the sensitivity to low-mass LLPs of this analysis with respect to gluon fusion searches. In the case of 15 GeV scalar LLPs, the improvement corresponds to a factor of 2 at a proper decay length of 30 mm.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Investigation of the Effect of Chrome and Nickel Concentrations During Two-Piston Splat Quenching of Austenitic Stainless Steels

For solidification rates at or near equilibrium solidification conditions the effects of chrome (Cr) and nickel (Ni) on stainless steel solidification modes and microstructures are well detailed. However, fusion-based additive manufacturing (FBAM) processes that rely on faster, more rapid solidification rates call for a more in-depth understanding of the effects of rapid solidification on the solidification behavior and how these change with variations in alloy composition. Eleven custom stainless steel (SS) alloys with unique compositions based on 316L were made using targeted alloying element additions to generate feedstock with Cr/Ni eq ratios ranging from 0.9 to 2.1. Two-piston splat quenching (SQ) was used to produce rapid solidification conditions similar to those achieved in powder bed fusion processes in a fraction of the time and cost of traditional methods. Employing heat transfer simulations, SEM, TEM, and STEM characterization techniques, the SQ process was found to consistently produce solidification rates estimated to be between ~ 0.4 and 1.6 m/s. Five unique solidification microstructures were identified within the rapidly solidified SQ samples (primary austenite, massively transformed ferrite to austenite, primary austenite and massively transformed ferrite to austenite, primary ferrite, and primary ferrite and massively transformed ferrite to austenite). Both the primary ferrite solidification mode and primary ferrite phase were found to form at lower Cr/Ni eq values than previously predicted. SQ samples with compositions that were within the compositional specifications for 316L SS, an alloy which is commonly used in FBAM processes, demonstrated a wider range of potential solidification modes and microstructures that could form at rapid solidification rates than expected. Finally, by using SQ as a means to simulate rapid solidification conditions similar to those observed in FBAM processes, potential new alloy compositions can be screened faster and more cost effectively than purchasing and running test batches of the metallic powder.

36 MATERIALS SCIENCE↗

Experimental Evaluation of Interfacial Bonding Strength Between 304 Stainless Steel Substrate and Electrodeposited Nickel Coating Using Mesoscale Mechanical Testing Methods

Electrodeposition is a commonly used method for depositing a metal layer on a metallic substrate, to provide a decorative finish or for functional purposes including wear and corrosion resistance. The interfacial bonding strength is a critical factor in determining the quality of electrodeposition, as it ensures the adhesion of the deposited layer to the substrate. Despite its importance, there has not previously been a suitable mechanical testing method to quantitatively characterize the bonding strength between the electrodeposited layers and the substrate, due to the high strength of the materials and to restrictions imposed by the geometry (due to the small thickness of the plating layer) to manufacture tensile bars. In this study, we introduce a novel mesoscale mechanical testing method to overcome these limitations. This technique was applied to assess the bonding strength between a 304 stainless steel (SS) substrate and electrodeposited nickel with three different plating formulae (nickel sulfamate, Watts bath, and hard nickel). The thickness of the pure nickel coatings achieved for each of the three electrolyte solutions was approximately 1 mm on each side of the substrate. Mesoscale tensile bars of 1 mm length were manufactured by a femtosecond laser, with the material interface at the center of the gauge section, and then tensile-tested with digital image correlation. Further, the results proved that the electrodeposition technique is able to produce a very high bonding strength that is close to the yield strength of both the substrate material and the electrodeposited nickel layer. Additionally, in the case of the Watts bath formula, the interfacial bonding strength between the SS 304 and electrodeposited nickel can exceed that of the nickel layer. This method is expected to be useful for quantifying the interfacial bonding strength in numerous applications.

36 MATERIALS SCIENCE↗

Pitting behavior of friction stir repair-welded 304L stainless steel in 3.5% NaCl solution at room temperature: role of grain and defect structures

Stainless steel (SS) canisters used for storing spent nuclear waste are prone to chloride-induced stress corrosion cracking. Friction stir welding (FSW), being a low heat input process, can be used for repair welding of these canisters. In this study, an artificial crack was introduced on the 304L SS coupons by an electric discharge machining process. The artificial crack was repair-welded by FSW by maintaining the tool temperature a constant at two levels (725 and 825 °C). Friction stirring significantly reduced the grain size of the stirred zone (SZ) from about 47 to 2–4 μm. The fraction of low-angle grain boundaries increased in the SZ from 2 to 37–43%. Here, on the other hand, the fraction of special grain boundaries (Σ3 and Σ9) that was ~ 50% in the base metal reduced to < 10% in the SZ. During friction stirring, the oxide layer of artificial crack was broken and aligned to form a spiral defect called lazy-S structure. All these microstructural changes affected the corrosion behavior of the FSW specimens when tested in 3.5% NaCl at room temperature using cyclic polarization, chronoamperometry, and electrochemical impedance spectroscopy. The FSW specimens showed lower polarization resistance and lower transpassive potential than those of the base metal specimens. However, the pitting protection potentials of the FSW specimens were higher than that of the base metal. The pitting behavior of the FSW specimens was influenced more by the preferential attack on the lazy-S region than by passive film breakdown. The flat band potentials of the passive film formed on the FSW specimens were more positive than that of base metal. The charge carrier density of passive film formed on the FSW specimens was higher than that of the base metal. The higher fraction of low-angle grain boundaries present in the FSW specimens could supply more number of misorientation dislocations at the metal/film interface which could form anion vacancies by a climb process leading to formation of oxide at these locations without stressing the substrate. Therefore, low-angle boundaries are considered helpful for formation of stress-free passive films that will be highly stable and enhance both pitting and stress corrosion cracking resistance.

Dry storage canister↗

The origin and formation of oxygen inclusions in austenitic stainless steels manufactured by laser powder bed fusion

The origins of nano-scale oxide inclusions in 316L austenitic stainless steel (SS) manufactured by laser powder bed fusion (L-PBF) was investigated by quantifying the possible intrusion pathways of oxygen contained in the precursor powder, extraneous oxygen from the process environment during laser processing, and moisture contamination during powder handling and storage. When processing the fresh, as-received powder in a wellcontrolled environment, the oxide inclusions contained in the precursor powder were the primary contributors to the formation of nano-scale oxides in the final additive manufactured (AM) product. These oxide inclusions were found to be enriched with oxygen getter elements like Si and Mn. By controlling the extraneous oxygen level in the process environment, the oxygen level in AM produced parts was found to increase with the extraneous oxygen level. The intrusion pathway of this extra oxygen was found to be dominated by the incorporation of spatter particles into the build during processing. Moisture induced oxidation during powder storage was also found to result in a higher oxide density in the AM produced parts. SS 316L powder free of Si and Mn oxygen getters was processed in a well-controlled environment and resulted in a similar level of oxygen intrusion. Finally, microhardness testing indicated that the oxide volume fraction increase from extraneous oxygen did not influence hardness values. However, a marked decrease in hardness was found for the humidified and Si-Mn free AM processed parts.

36 MATERIALS SCIENCE↗

Tailoring material microstructure and property in wire-laser directed energy deposition through a wiggle deposition strategy

Developing effective strategies to directly control material microstructure, property, and anisotropy is an active research area in metal additive manufacturing. This work develops a wiggle deposition pattern for wire-laser directed energy deposition (DED) of 316L stainless steel (SS) to modify the solidification texture, particularly in the building direction, in as-deposited samples. Through multi-physics simulation, operando near-infrared imaging, and synchrotron x-ray characterization, it is found that the wiggle deposition strategy induces highly dynamic melt flow and oscillating thermal gradient in the melt pool, which is responsible for the variation of preferable grain growth direction and crystallographic texture in the sample. The specific texture reduces the anisotropy in the tensile strength of as-printed 316L SS samples cut along different directions. Also, it largely increases the ductility along the build direction. Crystal plasticity simulation is performed to correlate the sample texture with mechanical property. In conclusion, this work offers a unique approach for tailoring local properties through the control of melt pool instability by applying different tool paths.

36 MATERIALS SCIENCE↗

Highly efficient interface stabilization for ambient-temperature quasi-solid-state sodium metal batteries

Solid-state sodium (Na) batteries (SSSBs) using sulfide-based solid electrolytes (SSEs) hold tremendous promise due to their high theoretical specific capacity, enhanced safety and abundant resources. However, detrimental interfacial issues between SSEs and Na metal present a major challenge to the advancement of sulfide-based SSSBs. To address interfacial issues, we demonstrate an efficient approach by incorporating an ionic liquid electrolyte ((PYR/Na)TFSI) as interlayer to stabilize the Na metal/SSE interface. The presence of the (PYR/Na)TFSI interlayer enables the formation of a stable solid electrolyte interphase (SEI) to prevent the harmful reactions and inhibit Na dendrites. Combination of ab initio molecular dynamics simulations and X-ray photoelectron spectroscopy revealed that this stable SEI is largely composed of reduced products of TFSI -, such as NaF and CF 3 . As a result, the symmetric cells exhibited stable Na plating/striping cycling for 300 h at 0.1 mA cm -2 . In addition, FeS2||Na quasi-solid-state batteries delivered an impressive specific capacity of over 300 mAh g -1 under the current density of 20 mA g -1 at room temperature. Under a higher current density (100 mA g -1 ), such batteries performed with long-term cycling stability and maintained a specific capacity of around 103 mAh g -1 after 330 cycles. This work demonstrates the novel perspective of using an ionic liquid interlayer to address interfacial issues, contributing to the advancement of high-performance SSSBs for the next-generation energy storage systems.

25 ENERGY STORAGE↗

Early reactivity of sodium silicate-activated slag pastes and its impact on rheological properties

The fast loss of fluidity of sodium silicate-activated slag (SS-AAS) systems have been widely studied in the literature. In this study, the rheology of these cements has been correlated with the evolution of the reaction products formed over time. For this purpose, a combination of experimental characterization techniques, to study the pore solution composition and microstructure of SS-AAS pastes and thermodynamic calculations have been applied. The initial precipitation of ill-defined N-A-S-H and C-N-A-S-H producta leads to a fast increase of the storage modulus after 40 min of reaction. These products are formed from the reaction of the Na{sup +} ions and silicate ions of the activator with the Ca{sup 2+} and aluminate species dissolved from the slag. However, when a shear is applied, the structure breaks down and fluidity is recovered, that infers that the attractive forces between the particles are low at the early stages of hydration.

36 MATERIALS SCIENCE↗

Nanostructural evolution of Al(OH)3 gel formed by the cubic and orthorhombic ye'elimite clinkers of calcium sulfoaluminate cements in an ultra-wide hydration temperature range

This paper investigated the influence of hydration temperature on the nanostructure of the AH{sub 3} phase formed in calcium sulfoaluminate cements. Orthorhombic ye'elimite (st-ye'elimite) and cubic ye'elimite (ss-ye'elimite) were hydrated in an ultra-wide temperature range (5–220 °C). Results showed that the AH{sub 3} phase formed by ss-ye'elimite was always microcrystalline in nature at various curing temperatures (5–130 °C), and transformed into the AlOOH phase at 150 °C and above. However, the AH{sub 3} phase formed by st-ye'elimite grew from a microcrystal to a favorable crystal as the temperature increased, and transformed into the AlOOH phase at 170 °C and above. The nanostructure of hydration products was further investigated using TEM/SAED analysis together with FE-SEM images, directly evidencing that the formed AFm-12 phase was single-crystal in nature, and the formed AH{sub 3} phase was microcrystalline at low temperatures and grew into single-crystal hexagonal prisms with the preferred growth direction along [001] direction at high temperatures.

36 MATERIALS SCIENCE↗

Hydrogen embrittlement of additively manufactured austenitic stainless steel 316 L

Additive manufacturing (AM) is a promising means of production of austenitic stainless steel (SS) parts for hydrogen service. The hydrogen embrittlement resistance of SS 316 L parts manufactured by powder-bed-fed selective laser melting (SLM) and directed energy deposition (DED) was examined using slow strain rate tensile testing. The influence of the hierarchical AM microstructures on mechanical response, microstructural evolution, and void formation were analyzed using multiscale electron microscopy. Furthermore, the presence of hydrogen reduced ductility in as-built DED materials, but did not significantly influence the response in as-built SLM material or heat-treated materials. Microstructural features driving these different responses are discussed.

36 MATERIALS SCIENCE↗

Promising performance of sulfide catholytes compared to halide alternatives in NMC811 cathodes for sheet-type sulfide solid-state batteries

Sulfide-based solid-state batteries (SSBs) show promise in achieving energy densities over 350 Wh/kg, yet challenges persist with their incorporation of high-voltage, nickel-rich layered oxide cathodes, such as LiNi₀.₈Mn₀.₁Co₀.₁O₂ (NMC811), due to the poor oxidation stability of sulfide solid-state electrolytes (SSEs) like Li₆PS₅Cl (LPSCl). Although halide SSEs such as Li₃InCl₆ (LIC) and Li₃YCl₆ (LYC) have previously shown promise in stabilizing high-voltage NMC cathodes, our research reveals that sulfide SSE catholytes, particularly when combined with surface-coated NMC cathodes, deliver superior performance. Here, this investigation assesses the cycling stability of various catholytes—LPSCl, LIC, Li₁₀GeP₂S₁₂ (LGPS), combined LIC-LPSCl, and LYC-LPSCl—in SSBs with LiNbO₃-coated NMC811 cathodes against sheet-type LPSCl separators. Findings indicate that while LGPS-based cathodes maintain higher capacity retention, they yield lower deliverable capacity, and LIC cathodes experience significant electrochemical degradation. Importantly, our results underscore that sulfide SSE catholytes, in conjunction with LiNbO₃-coated cathodes, optimize the cathode-electrolyte interphase (CEI), enhancing both kinetics and mass transport. These insights provide a strategic direction for optimizing catholyte composition in the development of sheet-type sulfide-based SSBs.

Catholyte↗

Statistical chronometry of meteorites. I. A Test of 26 Al homogeneity and the Pb-Pb age of the solar system’s $t=0$

Here, we use rapidly cooled achondrites to test the assumption of 26 Al homogeneity in the solar nebula, by checking if there is a single value of t SS , the absolute “Pb-Pb” age of the Solar System’s t=0, that makes concordant their ages from the Al-Mg and Pb-Pb systems. We find that values t SS =4568.42 ± 0.24 Myr do make these ages concordant, and therefore the hypothesis of homogeneous 26 Al is not falsified. This age, defined to be when the solar nebula had ( 26 Al/ 27 Al) = 5.23 × 10 –5 , is significantly older than the ≈ 4567.3 Myr inferred from direct measurements of Pb-Pb ages in CAIs. Discrepancies between the Al-Mg and Pb-Pb chronometers in chondrules and CAIs have previously been interpreted as arising from heterogeneities in 26 Al, under the presumption that the Al-Mg and Pb-Pb systems in CAIs closed simultaneously. We examine this assumption and show that resetting is to be expected in CAIs. In particular, we quantitatively demonstrate that it is plausible that Pb-Pb ages of CAIs were reset at late times, without resetting the earlier Al-Mg ages, if they were transiently heated in the same manner as chondrules. We critically examine Pb-Pb isochrons, refining data and suggesting best practices for their calculation and reporting. We advocate reporting chronometry as times of formation after t=0 rather than absolute ages, as only the former is useful for astrophysical models of the solar nebula. We advocate averaging of multiple samples, rather than anchoring to individual meteorites, to improve precision.

79 ASTRONOMY AND ASTROPHYSICS↗

Influence of sampling frequency and estimation method on phosphorus load uncertainty in the Western Lake Erie Basin, Ohio, USA

Accurate estimates of nutrient loads are necessary to identify critical source areas and quantify the impact of management practices on pollutant export. Previous studies have investigated nutrient load estimate uncertainty, but they often focus on nutrient loads estimated using an interpolation method for large-scale watersheds with short-term datasets. The study objective was to quantify uncertainty in soluble reactive phosphorus (SRP), total phosphorus (TP), and suspended solids (SS) load estimates from two small (<10 3 km 2 ) agricultural watersheds in the western Lake Erie Basin resulting from different sampling frequencies. Each watershed had high temporal resolution datasets of discharge (15 min) and nutrient concentration (1 to 3 samples per day) collected over a 30-year period (1990–2020). Firstly, SRP, TP, and SS loads were calculated using the high temporal resolution datasets, which was assumed as “true loads”. Secondly, the high temporal concentration data were decomposed to semiweekly, weekly, biweekly, and monthly sampling and annual loads were estimated using four common load estimation methods to assess the effect of sampling frequency and load estimation method on load estimate error. Across the four different methods, the composite method had the lowest relative root mean square and absolute bias, but the rectangular interpolation method was the most precise. Furthermore, even with semiweekly sampling, the composite method resulted in an unacceptable level of precision (average imprecision = 39 %), while the interpolation method resulted in an unacceptable bias (average absolute bias = 16 %). Because neither method could provide acceptable accuracy and precision at the lowest decrease in sampling (e.t. semiweekly sampling), continued daily sampling is recommended in these watersheds.

54 ENVIRONMENTAL SCIENCES↗

Voltammetry measurements in lithium chloride-lithium oxide (LiCl–Li 2 O) salt: An evaluation of working electrode materials

Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

In-situ formation of stable interface towards Li-in anode for halide solid-state electrolyte

Halide-based solid-state electrolytes (SSEs) are promising candidates for next-generation all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and chemical stability. However, their poor interfacial compatibility with lithium metal anode and Li-In alloy significantly hinder practical application due to the requirement for a protective interlayer. In this study, a novel approach to overcome this limitation is presented by introducing iron (Fe) doping into Li 3 InCl 6 (LIC), which enables direct and stable contact with lithium-indium (Li-In) metal without a protective interlayer. Thermodynamic and computational analyses identified Fe 3+ as a suitable dopant based on its similar reduction potential to In 3+ and structural compatibility within the halide lattice. The synthesized 10 at. % Fe-doped LIC exhibits high phase purity, retained ionic conductivity, and notably improved interfacial stability. Full-cell tests using Fe-LIC achieve over 300 cycles with 80 % capacity retention. At the same time, symmetric Li-In/ Fe-LIC/ Li-In cells sustain over 500 h of operation, representing the first reported long-term cycling of LIC-based ASSLB without a protective interlayer. In conclusion, this work establishes Fe doping as an effective strategy to stabilize halide SSEs of In system against Li-In alloy, thereby simplifying cell architecture and advancing the development of safer, high-performance halide-based solid-state electrolytes.

Halide-based solid-state electrolytes↗

Evaluation of residual stresses in isothermal friction stir welded 304L stainless steel plates

Friction stir welding was performed on 304L SS plates in order to heal simulated cracks created by electrical discharge machining. Two different tool temperatures (825 and 725 °C) were chosen for this study. Both neutron diffraction and X-ray diffraction techniques were employed to evaluate the residual stresses along two orthogonal reference directions, longitudinal (syy) and transverse (sxx). The former technique was also used to measure residual stresses at various depths. It was found that, at 1 mm depth from the top surface inside the stir zone (SZ), the longitudinal component was tensile in nature while the transverse component was compressive. The nature and magnitude of the residual stress fields, and the position of the peak residual stresses were found to vary with the weld depth. The SZ of the 725 °C weld exhibited higher peak stress than 825 °C weld mainly due to a lack of stress relief at the lower temperature.

Friction stir welding, Steel↗

On the thermal coarsening and transformation of nanoscale oxide inclusions in 316L stainless steel manufactured by laser powder bed fusion and its influence on impact toughness

The thermal evolution of nanoscale oxide inclusions in 316L stainless steel (SS) manufactured by laser powder bed fusion additive manufacturing (AM) was explored. The size, chemical composition, morphology, and distribution of the oxides were characterized as the function of heat treatment conditions. The study revealed the mechanistic driving force of the rapid oxide coarsening during recrystallization. Ostwald ripening governs oxide coarsening. The active grain boundary-oxide interaction at the early stage of recrystallization accelerated oxide coarsening via enhanced solute diffusion along grain boundaries. Pipe diffusion along dislocation cellular boundaries has a negligible contribution to oxide coarsening. At high temperatures (T> 1065 °C), although lattice diffusion primarily controlled the oxide growth, the contribution from the grain-boundary diffusion was necessary. The transformation from MnSiO 3 to CrMn 2 O 4 took place in the un-recrystallized grains but was not observed when recrystallization started. The interaction of grain boundary and oxides during recrystallization resulted in a high fraction of oxides accumulated at grain boundaries. While oxide coarsening does not significantly alter the toughness value, grain-boundary oxides promote microvoid formation and intergranular fracture under Charpy impact in the recrystallized AM 316L SS.

36 MATERIALS SCIENCE↗