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At least 973 records · Page 54

Activation of Semicore Electrons in Alkali Metals and Their Role in the B1–B2 Phase Transition under Pressure

Alkali fluorides are often thought of as archetypical ionic compounds whose structures can be understood in terms of the packing of rigid spheres. At ambient pressure, they assume the rocksalt (B1) structure, while under only a few GPa of pressure, the cesium chloride (B2) structure, with higher coordination numbers, is assumed for KF, RbF, and CsF. NaF requires almost 10 times more pressure to undergo this same phase transition, which has not been observed for LiF. Herein, we provide a detailed analysis, based upon quantum chemical calculations, explaining this behavior. We show that for the heavier alkali metals, the semicore p orbitals engage in metal-metal bonding in the B2 phase, facilitating the pressure-induced B1 → B2 structural transition. Furthermore, these findings suggest that the semicore orbitals of heavy alkali metals can be activated without the need of strong oxidants at very mild levels of compression, resulting in the formation of chemical bonds, challenging both traditional and modern core-valence distinctions. In addition, we argue that Cs 5p-5p bonding in CsCl occurs already at ambient pressure, stabilizing the B2 phase, and suggest experiments that may be able to detect signatures of such bonding.

Anions↗

Assessing the Sensitivity of Pourbaix Diagrams to Computational Protocols: Electrochemical Stability of Ni Oxides as a Case Study

Pourbaix diagrams stand as a useful tool in assessing and visualizing materials’ electrochemical stability and are widely used for electrocatalyst design. However, their reliability hinges on the accuracy of the chemical potentials of involved phases, which may bear uncertainties and can be significantly impacted by decision-making steps in the computational protocol. Here, this study introduces a robust sensitivity analysis framework, exemplified through a detailed examination of the computational Pourbaix diagram of Ni, the oxides of which are used as high-activity and cost-friendly catalysts for many electrochemical reactions. Quantities of interest derived from the Pourbaix diagram include the appearance and stability domain of the catalytically active Ni oxide phases along with the onset electrochemical potentials of phase transitions. These metrics can guide the design of operational conditions for Ni oxide electrocatalysts. We find that the employed DFT exchange-correlation functional has the most significant influence on the computed Pourbaix diagram. Uncertainties on crystal structures, along with their related ab initio energetics, are also found to affect the size of the phase stability domain. Higher-order coupling among input parameters is found to play a crucial role in influencing the appearance and distribution of Ni phases in the diagram. Our findings suggest a need to consider variations and uncertainties associated with the computational procedures on predicted Pourbaix diagrams for materials design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flight Measurements of the Flying Qualities of a Lockheed P-80A Airplane (Army No. 44-85099): Longitudinal-Stability and -Control Characteristics

This report contains the flight-test results of the longitudinal-stability and -control phase of a general flying qualities investigation of the Lockheed P-80A airplane (Army No. 44-85099). The tests were conducted at indicated airspeeds up to 530 miles per hour (0.76 Mach number) at low altitude and up to 350 miles per hour (0.82) Mach number) at high altitude. These tests showed that the flying qualities of the airplane were in accordance with the requirements of the Army Air Forces Stability and Control Specification except for excessive elevator control forces in maneuvering flight and the inadequacy of the longitudinal trimming control at low airspeeds.

Anderson, Seth B.↗

Thermodynamics of Minerals Stable near Earth's Surface

Project “Thermodynamics of Minerals Stable Near the Earth’s Surface” uses specialized calorimetric techniques to obtain new thermochemical data for solid phases of interest in the Earth’s “critical zone”, the near surface regions of the planet most directly affecting and affected by human activity. Major activity was in three areas: manganese oxide materials, aluminum clusters which are precursors to aluminum oxyhydroxide precipitates, and zeolites. All these classes of minerals are potential carriers of heavy metals and radionuclides in the environment, both within their crystal structures and as adsorbed layers or colloids. Their thermodynamic stability, as well as the sequence of stability of competing phases, governs the aqueous solubility of contaminants (and nutrients) in soil, groundwater, and sediments. The thermodynamics of these phases is strongly affected by particle size and crystallinity, since they often occur as very fine particles which do not coarsen in the near-surface environment. Many of these materials exhibit extensive polymorphism, multicomponent solid solution, and variable hydration states. Thus, one must define and systematize important thermodynamic variables, since one cannot make measurements on each and every possible phase, particle size, and composition. A major finding of the work on manganese oxides was labile water-induced oxidation-reduction reactions. These will be studied further by a combination of thermodynamic and synchrotron-based spectroscopic methods, the latter in collaboration with Peggy O’Day at UC Merced. The adsorption of other species, including simple organics, on such redox-active surfaces will also be investigated by a combination of thermochemical and spectroscopic studies. Studies of the energetics of water adsorption on mineral surfaces will be expanded to emphasize the adsorption of CO2 and small organic molecules, relevant to soil, groundwater, and the subsurface environment. Gas adsorption calorimetry, immersion calorimetry, and solution calorimetry will be combined with appropriate analytical and spectroscopic techniques to obtain a comprehensive picture of the interactions and their energetics. The evolution of aqueous aluminum clusters to form aluminum oxyhydroxide precipitates will be studied in detail by a combination of calorimetric and structural methods applied to aqueous samples aged at room temperature. The energetics of new classes of clusters will be explored. The project addresses several common themes relevant to the broad mission of the Department of Energy. Thermochemical data for minerals stable near the Earth’s surface, though still incomplete, are essential for understanding both natural and anthropogenic processes that affect our very existence on this planet. Such data contribute to the fundamental underpinning for mitigation and management strategies for the extraction and use of energy. Fundamental thermodynamic and mechanistic understanding is required to model processes ranging from heavy metal pollution to nuclear waste disposal to climate change.

58 GEOSCIENCES↗

Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects

Abstract Grain growth is prevalent in nanocrystalline (NC) materials at low homologous temperatures. Solute element addition is used to offset excess energy that drives coarsening at grain boundaries (GBs), albeit mostly for simple binary alloys. This thermodynamic approach is considered complicated in multi‐component alloy systems due to complex pairwise interactions among alloying elements. Guided by empirical and GB‐segregation enthalpy considerations for binary‐alloy systems, a novel alloy design strategy, the “ pseudo‐binary thermodynamic ” approach, for stabilizing NC‐high entropy alloys (HEAs) and other multi‐component‐alloy variants is proposed. Using Al 25 Co 25 Cr 25 Fe 25 as a model‐HEA to validate this approach, Zr, Sc, and Hf, are identified as the preferred solutes that would segregate to HEA‐GBs to stabilize it against growth. Using Zr, NC‐Al 25 Co 25 Cr 25 Fe 25 HEAs with minor additions of Zr are synthesized, followed by annealing up to 1123 K. Using advanced characterization techniques— in situ X‐ray diffraction (XRD), scanning/transmission electron microscopy (S/TEM), and atom probe tomography, nanograin stability due to coupling self‐stabilization and solute‐GB segregation effects is reported in HEAs up to substantially high temperatures. The self‐stabilization effect originates from the preferential GB‐segregation of constituent HEA‐elements that stabilizes NC‐Al 25 Co 25 Cr 25 Fe 25 up to 0.5 T m ( T m –melting temperature). Meanwhile, solute‐GB segregation originates from Zr segregation to NC‐Al 25 Co 25 Cr 25 Fe 25 GBs; this results in further stabilization of the phase and grain‐size (≈14 nm) up to ≈0.58 and ≈0.64 T m , respectively.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

SU(4) Chiral Spin Liquid, Exciton Supersolid, and Electric Detection in Moiré Bilayers

We propose a moiré bilayer as a platform where exotic quantum phases can be stabilized and electrically detected. Moiré bilayers consist of two separate moiré superlattice layers coupled through the interlayer Coulomb repulsion. In the small distance limit, an SU(4) spin can be formed by combining layer pseudospin and the real spin. As a concrete example, we study an SU(4) spin model on triangular lattice in the fundamental representation. By tuning a three-site ring exchange term K ~ ( t 3 /U 2 ), we find the SU(4) symmetric crystallized phase and an SU (4) 1 chiral spin liquid at the balanced filling. We also predict two different exciton supersolid phases with interlayer coherence at imbalanced filling under displacement field. Especially, the system can simulate an SU(2) Bose-Einstein condensation by injecting interlayer excitons into the magnetically ordered Mott insulator at the layer polarized limit. Smoking gun evidences of these phases can be obtained by measuring the pseudospin transport in the counterflow channel.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Flight Measurements of the Flying Qualities of a Lockheed P-80A Airplane (Army No. 44-85099): Lateral- and Directional-Stability and Control Characteristics

This report contains the flight-test results of the lateral and directional-stability and control phase (including tests with wing-tip tanks) of a general flying-qualities investigation of the Lockheed P-80A airplane (Army No. 44-85099). These tests were conducted at indicated airspeeds up to 494 miles per hour (0.691 Mach number) at low altitude and up to 378 miles per hour (0.816 Mach number) at high altitude. These tests showed that the flying qualities of the airplane were for the most part in accordance with the requirements of the Army Air Forces Stability and Control Specifications. The only major deficiency noted was the negative lateral stability with the wing-tip tanks installed.

Anderson, Seth B.↗

Application of matrix singular value properties for evaluating gain and phase margins of multiloop systems

A stability margin evaluation method in terms of simultaneous gain and phase changes in all loops of a multiloop system is presented. A universal gain-phase margin evaluation diagram is constructed by generalizing an existing method using matrix singular value properties. Using this diagram and computing the minimum singular value of the system return difference matrix over the operating frequency range, regions of guaranteed stability margins can be obtained. Singular values are computed for a wing flutter suppression and a drone lateral attitude control problem. The numerical results indicate that this method predicts quite conservative stability margins. In the second example if the eigenvalue magnitude is used instead of the singular value, as a measure of nearness to singularity, more realistic stability margins are obtained. However, this relaxed measure generally cannot guarantee global stability.

Mukhopadhyay, V.↗

Electrical Transport Interplay with Charge Density Waves, Magnetization, and Disorder Tuned by 2D van der Waals Interface Modification via Elemental Intercalation and Substitution in ZrTe 3 , 2H-TaS 2 , and Cr 2 Si 2 Te 6 Crystals

Electrical transport in 2D materials exhibits unique behaviors due to reduced dimensionality, broken symmetries, and quantum confinement. It serves as both a sensitive probe for the emergence of coherent electronic phases and a tool to actively manipulate many-body correlated states. Exploring their interplay and interdependence is crucial but remains underexplored. This review integratively cross-examines the atomic and electronic structures and transport properties of van der Waals-layered crystals ZrTe 3 , 2H-TaS 2 , and Cr 2 Si 2 Te 6 , providing a comprehensive understanding and uncovering new discoveries and insights. A common observation from these crystals is that modifying the atomic and electronic interface structures of 2D van der Waals interfaces using heteroatoms significantly influences the emergence and stability of coherent phases, as well as phase-sensitive transport responses. In ZrTe 3 , substitution and intercalation with Se, Hf, Cu, or Ni at the 2D vdW interface alter phonon–electron coupling, valence states, and the quasi-1D interface Fermi band, affecting the onset of CDW and SC, manifested as resistance upturns and zero-resistance states. We conclude here that these phenomena originate from dopant-induced variations in the lattice spacing of the quasi-1D Te chains of the 2D vdW interface, and propose an unconventional superconducting mechanism driven by valence fluctuations at the van Hove singularity, arising from quasi-1D lattice vibrations. Short-range in-plane electronic heterostructures at the vdW interface of Cr 2 Si 2 Te 6 result in a narrowed band gap. The sharp increase in in-plane resistance is found to be linked to the emergence and development of out-of-plane ferromagnetism. The insertion of 2D magnetic layers such as Mn, Fe, and Co into the vdW gap of 2H-TaS 2 induces anisotropic magnetism and associated transport responses to magnetic transitions. Overall, 2D vdW interface modification offers control over collective electronic behavior, transport properties, and their interplays, advancing fundamental science and nanoelectronic devices.

2D van der Waals interfaces↗

Structural Complexity and Tuned Thermoelectric Properties of a Polymorph of the Zintl Phase Ca 2 CdSb 2 with a Non-centrosymmetric Monoclinic Structure

The Zintl phase Ca 2 CdSb 2 was found to be dimorphic. Besides the orthorhombic Ca 2 CdSb 2 (-o), here we report on the synthesis, the structural characterization, and the thermoelectric transport properties of its monoclinic form, Ca 2 CdSb 2 (-m), and its Lu-doped variant Ca 2–x Lu x CdSb 2 (x ≈ 0.02). The monoclinic structure exhibits complex structural characteristics and constitutes a new structure type with the non-centrosymmetric space group Cm (Z = 30). The electrical resistivity ρ(T) measured on single crystals of both phases portrays a transition from a semiconductor to a degenerate p-type semiconductor upon doping with Lu and with an attendant change in the Hall carrier concentration nH from 7.15 × 10 18 to 2.30 × 10 19 cm –3 at 300 K. The Seebeck coefficient S(T) of both phases are comparable and indicate a hole-dominated carrier transport mechanism with magnitudes of 133 and 116 μV/K at 600 K for Ca 2 CdSb 2 (-m) and Ca 2–x Lu x CdSb 2 , respectively. The convoluted atomic bonding with an attendant large unit cell volume of ~4365 Å 3 drives a putative low thermal conductivity in these materials resulting in a power factor PF of 1.63 μW/cm K 2 and an estimated thermoelectric figure of merit zT of ~0.5 for Ca 2–x Lu x CdSb 2 at 600 K. Furthermore, differential scanning calorimetry results reveal the stability of these phases up to about 960 K, making them candidates for moderate temperature thermoelectric materials.

36 MATERIALS SCIENCE↗

Directed Self-Assembly of the Organic Semiconductor C8-BTBT-C8 in Anodic Aluminum Oxide Nanopores

Controlling the self-assembly of organic semiconductors at the nanoscale is critical for advancing high-performance electronic and photonic devices, yet it remains challenging due to their intrinsic anisotropic crystallization and sensitivity to processing conditions. Here, in this study, we demonstrate that cylindrical nanoconfinement within anodic aluminum oxide membranes provides a versatile platform to precisely tune the molecular orientation and phase behavior of the prototypical organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8). Combining temperature-dependent high-resolution synchrotron X-ray scattering with optical birefringence measurements, we uncover that confinement geometries (pore diameters 25–180 nm) and surface chemistry govern the emergence of distinct smectic A textures, featuring molecular layers either parallel or perpendicular to the pore axis. The competition between axial and radial smectic layering is modulated by pore size, surface hydrophilicity, and thermal history, enabling reversible control over domain orientations and transitions between liquid crystalline and crystalline states. Notably, nanoconfinement stabilizes the smectic phase over an expanded temperature range compared to bulk, while inducing complex multidomain configurations owing to geometric constraints and anchoring conditions. Our results elucidate fundamental mechanisms by which anisotropic nanoscale confinement directs the self-organization of highly conjugated organic molecules, with implications for optimizing directional charge transport and anisotropic optical responses in organic–inorganic hybrid nanoarchitectures. This study establishes nanoconfinement as a powerful strategy to engineer morphology and functional properties in organic semiconducting materials with nanoscale precision.

36 MATERIALS SCIENCE↗

The Efficacy of Replacing Metallic Cerium in Aluminum–Cerium Alloys with LREE Mischmetal

The ongoing development of aluminum–cerium alloys has produced materials exhibiting elevated temperature mechanical property retention, long term microstructural stability, and flexible processability compared to traditional aluminum alloys, accommodating the growing demand for high temperature aluminum alloys not requiring the use of high-cost elements like scandium. To date, reported Al–Ce alloy compositions contain large amounts of elemental cerium. Mischmetal (MM), a mixture of lanthanum, cerium, and other light rare earth elements (LREE) is less expensive and more available than pure cerium. The chemical similarity of the LREEs means there is possibility to use MM as the primary alloy addition, lowering alloy cost. This talk will report the effect of using MM instead of cerium in a 12 wt% binary alloy on mechanical properties, phase constituency, thermal stability, and load sharing. Results will show that MM can be substituted completely for cerium with a mostly positive impact on alloy performance.

Sims, Zachary↗

Disorder-induced time effect in the antiferromagnetic domain state of Fe 1+ y Te

Herein we report on temperature-dependent soft X-ray absorption spectroscopy (XAS) measurements utilizing linearly polarized synchrotron radiation to probe magnetic phase transitions in iron-rich Fe 1+y Te (y ≈ 0.12). X-ray magnetic linear dichroism (XMLD) signals, which sense magnetic ordering processes at surfaces, start to increase monotonically below the Néel temperature T N = 57 K. This increase is due to a progressive bicollinear antiferromagnetic (AFM) alignment of Fe spins of the monoclinic Fe 1+y Te parent phase. This AFM alignment was achieved by a [1 0 0]-oriented biasing field favoring a single-domain state during cooling across T N . Our specific heat and magnetization measurements confirm the bulk character of this AFM phase transition. On longer time scales, however, we observe that the field-biased AFM state is highly unstable even at the lowest temperature of T = 3 K. After switching off the biasing field, the XMLD signal decays exponentially with a time constant τ = 1506 s. The initial XMLD signal is restored only upon repeating a cycle consisting of heating and field-cooling through T N . We explain the time effect by a gradual formation of a multi-domain state with 90° rotated AFM domains, promoted by structural disorder, facilitating the motion of twin-domains. Significant disorder in our Fe 1+y Te sample is evident from our X-ray diffraction and specific heat data. The stability of magnetic phases in Fe-chalcogenides is an important material property, since the Fe(Te 1-x Se x ) phase diagram shows magnetism intimately connected with superconductivity.

36 MATERIALS SCIENCE↗

Development of Advanced Fuel Cell System (Phase 4)

A multiple-task research and development program was performed to improve the weight, life, and performance characteristics of hydrogen-oxygen alkaline fuel cells for advanced power systems. During Phase 4, the lowest stabilized degradation rate observed in all the testing completed during four phases of the program, 1 microvolt/hour, was demonstrated. This test continues after 5,000 hours of operation. The cell incorporates a PPf anode, a 90Au/10Pt cathode, a hybrid frame, and a Fybex matrix. These elements were developed under this program to extend cell life. The result demonstrated that the 80Au/20Pt cathode is as stable as a 90Au/10Pt cathode of twice the precious metal loading, was confirmed in full-scale cells. A hybrid frame two-cell plaque with dedicated flow fields and manifolds for all fluids was demonstrated to prevent the cell-to cell electrolyte transfer that limited the endurance of multicell plaques. At the conclusion of Phase 4, more than 90,900 hours of testing had been completed and twelve different cell designs had been evaluated. A technology base has been established which is ready for evaluation at the powerplant level.

Meyer, A. P.↗

Retrieval techniques: LVLH and inertially stabilized payloads

Procedures and techniques are discussed for retrieving payloads that are inertially or local vertical/local horizontal (LVLH) stabilized. Selection of the retrieval profile to be used depends on several factors: (1) control authority of the payload, (2) payload sensitivity to primary reaction control system (PRCS) plumes, (3) whether the payload is inertially or LVLH stabilized, (4) location of the grapple fixture, and (5) orbiter propellant consumption. The general retrieval profiles recommended are a V-bar approach for payloads that are LVLH or gravity-gradient stabilized, and the V-bar approach with one or two phase flyaround for inertially stabilized payloads. Once the general type of profile has been selected, the detailed retrieval profile and timeline should consider the various guidelines, groundrules, and constraints associated with a particular payload or flight. Reaction control system (RCS) propellant requirements for the recommended profiles range from 200 to 1500 pounds, depending on such factors as braking techniques, flyaround maneuvers (if necessary), and stationkeeping operations. The time required to perform a retrieval (starting from 1000 feet) varies from 20 to 130 minutes, depending on the complexity of the profile. The goals of this project are to develop a profile which ensures mission success; to make the retrieval profiles simple; and to keep the pilot workload to a minimum by making use of the automatic features of the orbiter flight software whenever possible.

Yglesias, J. A.↗

Solution-Phase Synthesis of PdH 0.706 Nanocubes with Enhanced Stability and Activity toward Formic Acid Oxidation

We report palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH 0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure–catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH 0.706 . On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. Furthermore, this work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗

Beta-Stabilized Ti-5Al-5Mo-5V-3Cr Primary and Secondary Phase Characterization using Ultrasonic Attenuation

Ti-5Al-5Mo-5V-3Cr (Ti-5553) is a beta-stabilized titanium alloy being evaluated for its use in additive manufacturing. The development of effective nondestructive characterization tools will be critical for successful insertion of Ti-5553 into applications. The microstructure of Ti-5553 can be modified significantly, through heat treatments alone, to produce single β-phase microstructure or dual α-β microstructure with variations on the types and quantities of the α phase in a β matrix. In this work, a set of heat treatments was chosen to obtain a range of microstructures, followed by an investigation of the ultrasonic response to gauge the degree to which these variations could be detected. Ultrasonic attenuation was selected because of its ability to detect differences in grain size and, potentially, the existence and limited details of secondary phases . Initial results show a very distinctive difference in attenuation between the single phase β and the α+β microstructures, and smaller, but still significant, differences among the α+β microstructures indicating that this approach merits further development.

ultrasonic attenuation, Ti-5Al-5Mo-5V-3Cr, heat tr↗