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At least 235 records · Page 13

Quantum critical point followed by Kondo-like behavior due to Cu substitution in the itinerant antiferromagnet La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7

La 2 ⁢Ni 7 is an itinerant magnetic system with a small ordered moment of ∼ 0.1⁢µ 𝐵 /Ni and a series of antiferromagnetic (AFM) transitions at 𝑇 1 = 61.0K, 𝑇 2 = 56.5K, and 𝑇 3 = 42.2K. 𝑀 ⁡(𝐻), and 𝜌 ⁡(𝐻) isotherms as well as constant field 𝑀⁡ (𝑇) and 𝜌 ⁡(𝑇) measurements on single-crystalline samples manifest a complex, anisotropic 𝐻−𝑇 phase diagram with multiple phase lines. Here, in this study, we present the growth and characterization of single crystals of the La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7 series for 0 ≤ 𝑥 ≤ 0.181. We measured powder x-ray diffraction and composition, as well as anisotropic temperature- and field-dependent resistivity, temperature- and field-dependent magnetization, and temperature-dependent heat capacity on these single crystals. Using the measured data we infer a transition temperature-composition (𝑇−𝑥) phase diagram for this system to study the evolution of the AFM ordering upon Cu substitution. For 0 ≤ 𝑥 ≤ 0.097, the system remains magnetically ordered at base temperature with 𝑥 ≤ 0.012, showing signs of multiple AFM ordering temperatures. For the higher substitution levels 0.125 ≤ 𝑥 ≤ 0.181, there are no signatures of magnetic ordering, but anomalous features in resistance and heat capacity data are observed which are consistent with the Kondo effect in this system. The intermediate 𝑥 = 0.105 sample lies between the magnetic ordered and the Kondo regime and is in the vicinity of the AFM quantum critical point (QCP). Thus, La 2⁢ (Cu 𝑥 ⁢Ni 1−𝑥 ) 7 is an example of a small moment system that can be tuned through a QCP. Given these data combined with the fact that the La 2⁢ Ni 7 structure has kagomelike, Ni sublattices running perpendicular to the crystallographic 𝑐 axis, and a predicted 3⁢𝑑-electron flat band that contributes to the density of states near the Fermi energy, La 2 ⁢(Cu 𝑥 ⁢Ni 1−𝑥 ) 7 becomes a promising system to host and study exotic physics.

Das, Atreyee [Ames Laboratory, and Iowa State Univ↗

Effects of Co substitution on the structural and magnetic properties of Sr ( Ni 1 - x Co x ) 2 P 2

Although SrNi 2 P 2 adopts the common ThCr 2 Si 2 structure for T ≥ 325 K, being in an uncollapsed tetragonal state rather than a collapsed tetragonal version, it is a special case for the ThCr 2 Si 2 class: on cooling below 325 K it adopts a one-third collapsed orthorhombic phase where one out of every three P rows bonds across the Sr layers. On the other hand, SrCo 2 P 2 only exhibits the uncollapsed ThCr 2 Si 2 structure from room temperature down to 1.8 K. Regardless of their low-temperature structures, neither SrNi 2 P 2 nor SrCo 2 P 2 manifests magnetic transitions down to 50 mK and 2 K, respectively. In this work we report the effects of Co substitution in Sr(Ni 1 - x Co x ) 2 P 2 , which allows for tuning the transition between the one-third collapsed and the uncollapsed structure. We find a rapid decrease of the one-third collapsed structural transition temperature with increasing Co fraction, until reaching full suppression for x ≥ 0.1. Substitution levels in the range 0.11 ≤ x ≤ 0.58 show no signs of any transition down to 1.8 K in the magnetization or resistance measurements in the range 1.8 ≤ T ≤ 300 K. However, different magnetically ordered states emerge for x ≥ 0.65, and disappear for x ≥ 0.99, recovering the known paramagnetic properties of the parent compound SrCo 2 P 2 . Further, these results are summarized in a phase diagram, built upon the characterization by energy dispersive x-ray spectroscopy, x-ray diffraction, temperature-dependent resistance, and field- and temperature-dependent magnetization measurements done on single crystals with different Co fraction. Both the magnetic and structural properties are compared to other systems with ThCr 2 Si 2 structure that exhibit magnetic ordering and collapsed tetragonal transitions. The magnetic ordering and moment formation are well described by Takahashi's spin fluctuation theory of itinerant electron magnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Incoherent electronic band states in Mn-substituted BaFe 2 As 2

Chemical substitution is commonly used to explore new ground states in materials, yet the role of disorder is often overlooked. In Mn-substituted BaFe 2 ⁢As 2 (MnBFA), superconductivity (SC) is absent, despite being observed for nominal hole-doped phases. Instead, a glassy magnetic phase emerges, associated with the S = 5/2 Mn local spins. In this work, we present a comprehensive investigation of the electronic structure of MnBFA using angle-resolved photoemission spectroscopy (ARPES). We find that Mn causes a small and orbital-specific reduction of the electron pockets, only partially disrupting nesting conditions. Based upon the analysis of the spectral properties, we observe, for all bands, an increase in the electronic scattering rate as a function of Mn content. This is interpreted as increasing band incoherence, which we propose as the primary contributor to the suppression of the magnetic order in MnBFA. Further, this finding connects the MnBFA electronic band structure properties to the glassy magnetic behavior observed in these materials and suggests that SC is absent because of the collective magnetic impurity behavior that scatters the Fe-derived excitations. Additionally, our analysis shows that the binding energy (E B ) dependence of the imaginary part of the self-energy [Im⁡Σ⁡(E B )] is best described by a fractional scaling (Im⁡Σ⁡(E B )∝$\sqrt-E_{B}$). These results indicate that Mn tunes MnBFA into an electronic disordered phase between the correlated Hund's metal in BaFe 2 ⁢As 2 and the Hund's insulator in BaMn 2 ⁢As 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Superstructures and magnetic order in heavily Cu-substituted ( Fe 1 – x Cu x ) 1 + y Te

Most iron-based superconductors exhibit stripe-type magnetism, characterized by the ordering vector Q = ($\frac{1}{2},\frac{1}{2}$). In contrast, Fe 1+y Te, the parent compound of the Fe 1+y Te 1–x Se x superconductors, exhibits double-stripe magnetic order associated with the ordering vector Q = ($\frac{1}{2},0$). Here, we use elastic neutron scattering to investigate heavily Cu-substituted (Fe 1–x Cu x ) 1+y Te compounds and reveal that (1) for x ≳ 0.4, short-range magnetic order emerges around the stripe-type vector at Q = ($\frac{1}{2}$ ± δ, $\frac{1}{2}$ ± δ, $\frac{1}{2}$) with δ ≈ 0.05; (2) the short-range magnetic order is associated with a superstructure modulation at Q = ($\frac{1}{3},\frac{1}{3},\frac{1}{2}$), with the magnetic correlation length shorter than that for the superstructure; and (3) for x ≳ 0.55, we observe an additional intergrown phase with higher Cu content, characterized by a superstructure modulation vector Q = ($\frac{1}{3},\frac{1}{3},0$) and magnetic peaks at Q = ($\frac{2}{3},\frac{1}{3},\frac{1}{2}$)/($\frac{1}{3},\frac{2}{3},\frac{1}{2}$). The positions of superstructure peaks suggest that relative to the tetragonal unit cell of Fe 1+y Te, heavy Cu substitution leads to Fe-Cu orderings that expand the unit cell by $\sqrt{2}$ × 3$\sqrt{2}$ times in the ab plane, corroborated by first-principles calculations that suggest the formation of spin chains and spin ladders. Finally, our findings show that stripe-type magnetism is common in magnetically diluted iron pnictides and chalcogenides, despite the varying associated atomic orderings

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemical compression and ferroic orders in La substituted BiFe O 3

Chemical compression effects on the ferroic orders in La substituted BiFeO 3 are studied by atomic pair distribution function analysis and structure modeling. While rhombohedral BiFeO 3 exhibits ferroelectricity and antiferromagnetism (AF) with a cycloidal Fe spin arrangement leading to zero magnetization, La substituted BiFeO 3 exhibits a reduced lattice polarization, strengthened AF order, and an apparently suppressed spin cycloid leading to nonzero magnetization. Furthermore, the observed changes in the ferroic orders arise from the chemical compression induced changes in the octahedral rotation and ferroelectric displacement of Bi atoms, which appear as lattice degrees of freedom entangling the electronic and magnetic orders in BiFeO 3 .

36 MATERIALS SCIENCE↗

Crystal structures of 40- and 71-substitution variants of hydroxynitrile lyase from rubber tree

Hydroxynitrile lyase fromHevea brasiliensis(HbHNL) and the esterase SABP2 fromNicotiana tabacumshare the α/β-hydrolase fold, a Ser–His–Asp catalytic triad and 44% sequence identity, yet catalyze different reactions. Prior studies showed that three active-site substitutions inHbHNL conferred weak esterase activity. To investigate how regions beyond the active site influence catalytic efficiency and active-site geometry, we engineeredHbHNL variants with increasing numbers of substitutions to match SABP2. Variant HNL16 has all amino acids within 6.5 Å of the active site identical to SABP2, HNL40 those within 10 Å and HNL71 those within 14 Å. HNL16 exhibited poor esterase activity, whereas both HNL40 and HNL71 showed efficient esterase catalysis, demonstrating that residues beyond the immediate active site are critical for functional conversion. X-ray structures of HNL40 and HNL71 reveal a progressive shift in backbone positions toward those of SABP2, with r.m.s.d. values of 0.51 Å (HNL40) and 0.41 Å (HNL71) over the C α atoms, and even smaller r.m.s.d.s within the active-site region. Both HNL40 and HNL71 show a restored oxyanion hole and an additional tunnel connecting the active site to the protein surface. This work demonstrates the essential role of distant, indirectly acting residues to catalysis in α/β-hydrolase enzymes.

Biochemistry & Molecular Biology↗

Market Pricing and Settlements Analysis Considering Capacity Sharing and Reserve Substitutions of Operating Reserve Products

Electricity market pricing and settlement are the key signals for real-time dispatch and long-term investment decisions. Regional transmission operators (RTOs) in the U.S. adopt uniform pricing scheme, which is based on the marginal costs of supplying an incremental MW of electric services. The marginal cost of an electric service is highly dependent on the constraints in the pricing models of RTOs. A slight difference in constraint modeling of pricing model on energy and ancillary services could result in drastically different market clearing prices (MCPs), cleared reserve quantities, and associated revenue. RTOs in the U.S. have various market designs and assumptions in ancillary services modeling in capacity sharing and reserve substitutes. This paper examines four combination models of capacity sharing and reserve substitutes and analyzes the associated market implications. The numerical results present that 1) cascading reserve requirements have direct impact on reserve pricing schemes 2) both cascading reserve requirements and sharing capacity have significant impact on reserve MCPs and locational marginal prices, and thus result in drastically different reserve revenue, energy revenue, generation cost, and generation profit.

ancillary services↗

Static to inducibly dynamic stereocontrol: The convergent use of racemic β-substituted ketones

The synthesis of stereochemically complex molecules in the pharmaceutical and agrochemical industries requires precise control over each distinct stereocenter, a feat that can be challenging and time consuming using traditional asymmetric synthesis. Although stereoconvergent processes have the potential to streamline and simplify synthetic routes, they are currently limited by a narrow scope of inducibly dynamic stereocenters that can be readily epimerized. Furthermore, we report the use of photoredox catalysis to enable the racemization of traditionally static, unreactive stereocenters through the intermediacy of prochiral radical species. This technology was applied in conjunction with biocatalysts such as ketoreductases and aminotransferases to realize stereoconvergent syntheses of stereodefined γ-substituted alcohols and amines from β-substituted ketones.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of the ARTIC Version 3 and Version 4 SARS-CoV-2 Primers and Their Impact on the Detection of the G142D Amino Acid Substitution in the Spike Protein

The ARTIC Network provides a common resource of PCR primer sequences and recommendations for amplifying SARS-CoV-2 genomes. The initial tiling strategy was developed with the reference genome Wuhan-01, and subsequent iterations have addressed areas of low amplification and sequence drop out. Recently, a new version (V4) was released, based on new variant genome sequences, in response to the realization that some V3 primers were located in regions with key mutations. Herein, we compare the performance of the ARTIC V3 and V4 primer sets with a matched set of 663 SARS-CoV-2 clinical samples sequenced with an Illumina NovaSeq 6000 instrument. We observe general improvements in sequencing depth and quality, and improved resolution of the SNP causing the D950N variation in the spike protein. Importantly, we also find nearly universal presence of spike protein substitution G142D in Delta-lineage samples. Due to the prior release and widespread use of the ARTIC V3 primers during the initial surge of the Delta variant, it is likely that the G142D amino acid substitution is substantially underrepresented among early Delta variant genomes deposited in public repositories. In addition to the improved performance of the ARTIC V4 primer set, this study also illustrates the importance of the primer scheme in downstream analyses.

59 BASIC BIOLOGICAL SCIENCES↗

Substitution or Shared Utilization? Intrahousehold Vehicle Use in Mixed-Powertrain Households

While previous research has focused heavily on understanding the factors deriving alternative fuel vehicle adoption rates, there remains a significant gap in understanding how households distribute mileage across different powertrains. This study utilizes data from the 2022 Next Generation National Household Travel Survey to investigate vehicle miles traveled within a sample of 150 plug-in electric vehicle (PEV)-owning households (in which at least one battery electric vehicle is present), characterizing how different powertrains are integrated into daily mobility. Leveraging a Seemingly Unrelated Regression (SUR) framework the study jointly models the utilization of PEVs, hybrid electric vehicles (HEV), and internal combustion engine vehicles (ICEVs) while accounting for household-level substitution effects. The results provide evidence of an asymmetric substitution effect. In households with mixed-powertrain configurations, the ICEV captures a substantially higher share of household miles (compared with the PEV), acting as a utility sponge. Conversely, the model identifies specific socioeconomic and geographic cohorts that prioritize PEV as the primary household workhorse, indicating a systematic sorting effect. Although the sample size limits broader generalizability, these findings suggest that PEVs are used for frequent, specific routine-intensive roles, whereas the ICEV remains a specialized utility vehicle. These insights highlight distinct intrahousehold vehicle use behaviors that are often obscured by aggregate fleetwide statistics.

25 ENERGY STORAGE↗

Hole doping and electronic correlations in Cr substituted BaFe$_{2}$As$_{2}$

For a significant composition range, the suppression of the spin density wave transition temperature (T SDW ) in Cr- and Mn-substituted BaFe 2 As 2 (CrBFA and MnBFA, respectively) coincides as a function of Cr/Mn content, despite the distinct electronic effects of these substitutions. Additionally, for any Cr/Mn content superconductivity (SC) is absent and this topic is particularly less explored in the case of CrBFA. Here, in this work, we employ angle-resolved photoemission spectroscopy (ARPES) and combined density functional theory plus dynamical mean field theory (DFT+DMFT) to address the evolution of the Fermi surface (FS) and electronic correlations in CrBFA. Our findings reveal that incorporating Cr leads to an effective hole doping of the states near the FS, which is well described within the virtual crystal approximation (VCA). Moreover, analysis of the ARPES spectra of the bands with main d yz -orbital character reveals a fractional scaling of the imaginary part of self-energy as a function of the binding energy, a signature property of Hund's correlations. Our DFT+DMFT calculations support these experimental findings. We conclude that CrBFA is a correlated electron system for which the changes in the FS as a function of Cr are unrelated to the suppression of T SDW . In addition, we suggest that the absence of SC is primarily due to the competition between Cr local moments and the Fe-derived itinerant spin fluctuations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Calibrating Constant Elasticity of Substitution Technologies to Bottom-up Cost Estimates

We propose a method for calibrating an industry-level technology to engineering (bottom-up) estimates with a particular focus on abatement opportunities. As a demonstration, substitution elasticities across inputs are adjusted in the nested cost function for the electricity sector to best fit a target marginal abatement cost (MAC) curve derived from engineering assessments of available technologies. Elasticities are optimized over an entire relevant range of the MAC, whereas current techniques use local point estimates under little or no abatement. In the context of fitting to a given MAC we evaluate alternative nesting structures and find that, while complexity in nesting improves the fit, even relatively simple nesting structures can reasonably approximate the target MAC. In our example, focused on the electricity sector, we find standard elasticities adopted in top-down models moderately overstate abatement costs relative to the engineering targets. In our preferred specification the most important adjustment is to escalate the substitution elasticity between energy and value-added inputs. This is consistent with an argument that the current set of point estimates fail to properly account for new capital-based technologies. These conclusions, however, are sensitive to our assumption about output-intensity abatement and consumer price responsiveness, both of which are not delineated in engineering estimates.

abatement cost↗

Evaluation of Pozzolan-substituted Cast Stone for Pretreated Hanford Tank Waste

Portland cement. The future availability of quality Class F fly ash has come into question as coal-fired power plants are being converted to gas or taken offline. Consequently, alternative pozzolanic reagents are being evaluated for fly ash replacement in cementitious matrices for treating radioactive waste and debris. In 2023 and 2024, Savannah River National Laboratory (SRNL) was funded to evaluate natural pozzolans for the replacement of Class F fly in the Savannah River Site (SRS) Saltstone formulation. Based on the promising results and uncertain availability of Class F fly ash in the northwestern US, Hanford Tank Waste Operations & Closure, LLC (H2C) requested SRNL to evaluate the potential for substituting natural pozzolans in the Hanford West Area Pretreated Low Activity Tank Waste (PTW/LAW) Cast Stone formulation1 . Task 1 in this request was to determine the change in Cast Stone volume resulting from stabilization/solidification of 1 L of PTW/LAW tank waste. The densities of three (Hess Pumice, tephra pumice, and clinoptilolite zeolite) pozzolan-substituted Baseline Cast Stone mixes were determined, and volume changes relative to the fly ash-Baseline Mix with a water-to-dry mix = 0.40 were calculated.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of Al Substitution for Fe in Na₅FeSi₄O₁₂ (5.1.8) Glasses: Structure and Crystallization

In this study, the effects of substituting Al for Fe in 5Na2O∙(Al2O3)x∙(Fe2O3)1-x∙8SiO2 glass, x=0 to 1, and Na5AlxFe1-xSi4O12 (5.1.8) crystal, were investigated using thermal analysis, Fe K-edge X-ray absorption, X-ray diffraction, Raman spectroscopy, and Electron Probe Microanalysis. In both glass and crystallized glass, nearly all the Fe was tetrahedrally coordinated Fe3+, as expected from the high concentration of Na2O. The substitution of Al for Fe in the glasses caused the glass transition temperature to increase as polymerization increased, as evidenced by Raman, likely due to both field strength differences of Al vs Fe and a small amount of Fe2+ network modifier present with Fe. After heat treatment at 700 °C for 24 hours, the glasses had crystallized, forming Na2SiO3 and NaAlSiO4 in compositions with high Al concentrations and the 5.1.8 crystal in compositions with high Fe concentrations. Through electron microprobe, it was determined that <0.04 formula unit Al incorporated into the 5.1.8 crystal, i.e. Na5Fe0.96Al0.04Si4O12. The 5.1.8 crystal only formed when Fe concentration was higher than Al in the starting glass.

Antonio, Raine (ORCID:0009000634297975)↗

Incommensurate Antiferromagnetic Order in the Fe-substituted Bi-2201 Cuprate in the Heavily Overdoped Regime

Elastic neutron scattering experiments showed incommensurate antiferromagnetic peaks in 5% Fe-substituted Bi-2201 cuprate in the non-superconducting heavily overdoped regime. Here, the incommensurability δ ∼ 0.21 is comparable to that observed in Fe-substituted Bi-2201 in the overdoped regime. [Hiraka et al., Phys. Rev. B 81, 144501 (2010).] The magnetic correlation length is comparable between the overdoped and non-superconducting heavily overdoped regimes. It is plausible that incommensurate antiferromagnetic order is induced and stabilized by Fe in the heavily overdoped regime, which suggests a robust antiferromagnetic correlation beyond the superconducting dome in the phase diagram.

Bi-2201↗

Substitution of ceramics for high temperature alloys

The high temperature capability of ceramics such as silicon nitride and silicon carbide can result in turbine engines of improved efficiency. Other advantages when compared to the nickel and cobalt alloys in current use are raw material availability, lower weight, erosion/corrosion resistance, and potentially lower cost. The use of ceramics in three different sizes of gas turbine is considered; these are the large utility turbines, advanced aircraft turbines, and small automotive turbines. Special consideration, unique to each of these applications, arise when one considers substituting ceramics for high temperature alloys. The effects of material substitutions are reviewed in terms of engine performance, operating economy, and secondary effects.

Probst, H. B.↗

Substitution for chromium in 304 stainless steel

An investigation was conducted to determine the effects of substituting less strategic elements for Cr on oxidation and corrosion resistance of AISI 304 stainless steel. Cyclic oxidation resistance was evaluated at 870 C. Corrosion resistance was determined by exposure of specimens to a boiling copper-rich solution of copper sulfate and sulfuric acid. Alloy substitutes for Cr included Al, Mn, Mo, Si, Ti, V, Y, and misch metal. A level of about 12% Cr was the minimum amount of Cr required for adequate oxidation and corrosion resistance in the modified composition 304 stainless steels. This represents a Cr saving of 33 percent. Two alloys containing 12% Cr plus 2% Al plus 2% Mo and 12% Cr plus 2.65% Si were identified which exhibited oxidation and corrosion resistance comparable to AISI 304 stainless steel.

Stephens, J. R.↗

Reduction of chromium in Ni-base superalloys through element substitution and rapid solidification processing

The reduction in the use of Cr in Ni base superalloys by the combined approaches of both elemental substitution and rapid solidification processing is studied. The elements Si, Zr, Y and Hf were chosen as potential partial substitutes for Cr in Waspaloy and IN 713LC sine their separate addition to other alloys has previously resulted in enhanced oxidation resistance. The roles of Cr and these replacement elements in determining the microstructure and properties are evaluated. The elements Si, Zr, and Y and Hf are used as partial replacements for Cr in the base superalloys and these resultant alloys are processed using rapid solidification techniques. The mechanical properties and oxidation resistance of the processed materials are evaluated. The microstructure is characterized using state of the art techniques (e.g. analytical transmission electron microscopy), and the mechanism by which these structures are produced is determined.

Fraser, H. D.↗