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Crystal structure and magnetic properties of CeFe 11 M (M = Mo, W)

Tetragonal CeFe 11 Mo (struct. type ThMn 12 , a = 8.529(1) Å, c = 4.766(1) Å, V = 346.68(1) Å 3 ) and novel isostructural CeFe 11 W (a = 8.539(1) Å, c = 4.754(1) Å, V = 346.62(1) Å 3 ) are obtained in bulk, as homogenized single-phase arc-melted alloys. Here, their crystal structures are evaluated by full profile Rietveld analysis of the powder X-ray diffraction patterns which confirm that Ce occupies the 2a atomic site in both cases, whereas atomic disorder is present in the Fe-sublattice, i.e., predominantly on the dumbbell 8i site and minorly on two other sites 8j and 8f. In CeFe 11 Mo the third element, M, is mixed with Fe on the 8i dumbbell site and 8f atomic position, whereas in CeFe 11 W, M is mixed on the 8i and 8j Fe sites. In these bulk CeFe 12-x M x alloys the tetragonal structure persists at lower M content, x < 1 here, in comparison to known similar alloys, with x > 1. Because of the low M content, comparably higher values of mass magnetization and Curie temperature are achieved i.e., CeFe 11 Mo: ϭ s = 104 emu/g (14.7 µ B /f.u.), T c = 420 K and CeFe 11 W: ϭ s = 99 emu/g (16.5 µ B /f.u.), T c = 450 K. Magnetocrystalline anisotropy is uniaxial with anisotropy fields H a ∼ 14.5 and 16.5 kOe, respectively. Based on Curie temperature and magnetic anisotropy enhancements, using tungsten as the stabilizing dopant is more beneficial than molybdenum.

36 MATERIALS SCIENCE↗

Pressure induced irreversible phase transformation in an ordered high-entropy alloy

We report on a pressure induced irreversible phase transformation in an ordered eutectic high-entropy alloy (EHEA) AlCoCrFeNi2.1. The suction cast sample was synthesized by arc melting of raw elements resulting in an ordered B2 and FCC phase mixture for eutectic AlCoCrFeNi2.1 alloy. This phase mixture was confirmed by transmission electron microscopy (TEM) where superlattice reflections corresponding to ordered B2 phase were observed while the FCC phase remains disordered. The B2 phase was observed to be enriched in Nickel and Aluminum while the surrounding FCC phase is enriched in Fe, Cr and Co. The suction-cast EHEA sample was studied by X-ray diffraction under high pressure in a diamond anvil cell with platinum pressure marker to 73 GPa at ambient temperature. The B2 to FCC phase transformation is completed by 3 GPa in sharp contrast to BCC to FCC phase transition of 21 GPa in additively manufactured EHEA samples. The X-ray diffraction and TEM studies of pressure recovered samples show presence of only FCC grains without any specific orientation with respect to starting sample. These results are consistent with molecular dynamics simulations that the presence of B2 phase aids in the formation of the B2 to FCC phase transition under high pressures.

36 MATERIALS SCIENCE↗

Understanding the effect of refractory metal chemistry on the stacking fault energy and mechanical property of Cantor-based multi-principal element alloys

Multi-principal-element alloys (MPEAs) based on 3d-transition metals show remarkable mechanical properties. In this study, the stacking fault energy (SFE) in face-centered cubic (fcc) alloys is a critical property that controls underlying deformation mechanisms and mechanical response. Here, we present an exhaustive density-functional theory study on refractory- and copper-reinforced Cantor-based systems to ascertain the effects of refractory metal chemistry on SFE. We find that even a small percent change in refractory metal composition significantly changes SFEs, which correlates favorably with features like electronegativity variance, size effect, and heat of fusion. For fcc MPEAs, we also detail the changes in mechanical properties, such as bulk, Young's, and shear moduli, as well as yield strength. A Labusch-type solute-solution-strengthening model was used to evaluate the temperature-dependent yield strength, which, combined with SFE, provides a design guide for high-performance alloys. We also analyzed the electronic structures of two down-selected alloys to reveal the underlying origin of optimal SFE and strength range in refractory-reinforced fcc MPEAs. These new insights on tuning SFEs and modifying composition-structure-property correlation in refractory- and copper-reinforced MPEAs by chemical disorder, provide a chemical route to tune twinning- and transformation-induced plasticity behavior in fcc MPEAs.

36 MATERIALS SCIENCE↗

Structural characterization of highly alloyed (Al,Gd)N thin films

Highly alloyed (Al,Gd)N is of potential interest in a variety of applications, including neutron detection and in devices such as non-volatile memory. Gd has been shown to have very low equilibrium solubility in AlN at room temperature; however, non-equilibrium deposition techniques such as sputtering are able to deposit thin films, which incorporate large amounts of Gd. Here, we characterize a highly-alloyed (Al,Gd)N combinatorial thin film grown by RF sputtering on a GaN substrate, looking for any evidence of chemical or phase segregation or structural disorder in the films. Compositions with between 13% and 32% Gd (on a cation basis) were studied. No evidence was found for chemical or phase segregation in any studied composition. Higher degrees of Gd incorporation led to greater structural disorder in the film and a tendency toward amorphization; however, electron diffraction shows that the film does not become fully amorphous at any of the studied compositions, instead retaining textured local order even at 32% Gd. Electron energy loss spectra suggest that the material retains a locally wurtzite-like tetrahedral bonding environment at all studied compositions.

36 MATERIALS SCIENCE↗

Switching of Magnetic Order via Non‐Magnetic Al Addition in FeCoNiMnAl x Films

Magnetic high entropy alloys (HEAs) consisting of 3 d transition metals offer an exciting platform to explore novel magnetic phases as they often house competing exchange interactions in combination with random site disorders. In this work, a sensitive and tunable magnetic order is demonstrated in sputtered single-layer FeCoNiMnAl x films, as a function of non-magnetic Al addition, along with an unexpected exchange bias effect. Thin films of 50 nm FeCoNiMn exhibit a face-centered-cubic ( fcc ) phase, reentrant spin glass (SG) transition near 100 K, and a large exchange bias of over 500 Oe after field-cooling to 5 K. The exchange bias is increased to 930 Oe through a small addition of 5 at.% Al. Further Al addition to 12 at.% results in a body-centered-cubic ( bcc ) phase, coinciding with a large increase in the saturation magnetization, decrease of exchange bias to 50 Oe, and suppression of SG behavior. The change in magnetic order across the Al-induced structural transformation is mediated by the switching of Mn ground state from AF to FM, which is supported by first-principles calculations and experimentally confirmed via X-ray magnetic circular dichroism. These results open up new HEA strategies for explorations of novel magnetic phases.

competing exchange interactions↗

The Ductility of 49Fe-49Co-2V Soft Magnetic Alloy Bar: Surface Effects and Test Methods

The tensile ductility of 49Fe-49Co-2V (Hiperco® 50A) bar was investigated in both as-received and heat-treated conditions. The as-received/machined specimens exhibit very low ductility compared to samples where heat treatment was the final step prior to testing. Microstructural characterization showed that internal residual strain from bar processing and, most importantly, surface machining damage, cause lower elongation in the as-received material. Because fracture of this intermetallic alloy initiates at the surface, it is particularly susceptible to surface machining damage, i.e., the near-surface region has already exhausted most of its ability to accumulate tensile strain. During heat treatment, the internal residual strain and near-surface machining damage are eliminated and ductility is improved, despite a higher degree of crystallographic ordering in the heat-treated condition (which typically lowers ductility). Furthermore, if machining is again performed after heat treatment, the material again exhibits brittle behavior, even with only light touch-up machining passes. Here, in this work, methods of tensile strain measurement were investigated, namely conventional knife-edge extensometry and noncontact digital image correlation (DIC) on heat-treated material. For clip-on knife-edge extensometry, the range of failure strain was 2.5-5.5% for heat-treated Hiperco. For noncontact methods, ductility up to 7% was observed. The results highlight the tendency for the alloy to fail at surface imperfections, even those produced by application of the extensometer itself. Noncontact laser extensometry is recommended for determining the intrinsic ductility of the alloy. A method of laser surface modification was developed which increased ductility by ~ 100% compared to unmodified samples. The high cooling rates achieved during laser surface processing can bypass the ordering reaction and produce a ductile disordered structure at the surface that exhibits ductile fracture characteristics.

EBSD↗

Computer Code for Nanostructure Simulation

Due to their small size, nanostructures can have stress and thermal gradients that are larger than any macroscopic analogue. These gradients can lead to specific regions that are susceptible to failure via processes such as plastic deformation by dislocation emission, chemical debonding, and interfacial alloying. A program has been developed that rigorously simulates and predicts optoelectronic properties of nanostructures of virtually any geometrical complexity and material composition. It can be used in simulations of energy level structure, wave functions, density of states of spatially configured phonon-coupled electrons, excitons in quantum dots, quantum rings, quantum ring complexes, and more. The code can be used to calculate stress distributions and thermal transport properties for a variety of nanostructures and interfaces, transport and scattering at nanoscale interfaces and surfaces under various stress states, and alloy compositional gradients. The code allows users to perform modeling of charge transport processes through quantum-dot (QD) arrays as functions of inter-dot distance, array order versus disorder, QD orientation, shape, size, and chemical composition for applications in photovoltaics and physical properties of QD-based biochemical sensors. The code can be used to study the hot exciton formation/relation dynamics in arrays of QDs of different shapes and sizes at different temperatures. It also can be used to understand the relation among the deposition parameters and inherent stresses, strain deformation, heat flow, and failure of nanostructures.

Filikhin, Igor↗

Towards a Deeper Fundamental Understanding of (Al,Sc)N Ferroelectric Nitrides

Density functional theory (DFT) calculations, within the virtual crystal alloy approximation, are performed, along with the development of a Landau-type model employing a symmetry-allowed analytical expression of the internal energy and having parameters determined from first principles, to investigate properties and energetics of Al1-xScxN ferroelectric nitrides in their hexagonal forms. These DFT computations and this model predict the existence of two different types of minima, namely, the fourfold-coordinated wurtzite (WZ) polar structure and a five-fold coordinated paraelectric hexagonal phase (denoted as H5), for any Sc composition up to 40%. The H5 minimum progressively becomes the lowest-energy state within hexagonal symmetry as the Sc concentration increases from 0 to 0.4. Furthermore, the model points to several key findings. Examples include the crucial role of the coupling between polarization and strains to create the WZ minimum, in addition to polar and elastic energies, and that the origin of the H5 state overcoming the WZ phase as the global minimum within hexagonal symmetry when increasing the Sc composition mostly lies in the compositional dependency of only two parameters-one linked to the polarization and another one being purely elastic in nature. Other examples are that forcing Al1-xScxN systems to have no or a weak change in lattice parameters when heating them allows us to reproduce their finite-temperature polar properties well and that a value of the axial ratio close to that of the ideal WZ structure implies a large polarization at low temperatures but not necessarily at high temperatures because of the ordered-disordered character of the temperature-induced formation of the WZ state. Such findings should allow for a better fundamental understanding of (Al,Sc)N ferroelectric nitrides, which may be used to design efficient devices having, e.g., low operating voltages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An electron tunneling study of superconductivity in amorphous Sn(sub 1-x)Cu(sub x) thin films

The amorphous phase of Sn would have a superconducting transition temperature near 8 K, much higher than that of crystalline Sn with T(sub c) = 3.5 K. To obtain the amorphous phase, however, it is necessary to use a Sn alloy, usually Cu, and quench condense the alloy films onto a liquid He temperature substrate. Alloying with Cu reduces the superconducting transition temperature almost linearly with Cu concentration with an extrapolation of T(sub c) to zero for x = 0.85. Analysis of the tunneling characteristics between a normal metal electrode with an insulating barrier and superconducting amorphous Sn-Cu films provides detailed information on the changes in the electron-phonon coupling which determines T(sub c) in these alloys. The change from very strong electron-phonon coupling to weak-coupling with the increase in Cu content of amorphous Sn-Cu alloys for the range 0.08 is less than or equal to x is less than or equal to 0.41 is presented and discussed in terms of theories of electron-phonon coupling in disordered metals.

Naugle, D. G.↗

Ab Initio Simulations of Martensitic Phase Transformations in NiTi-based High Temperature Ternary Shape Memory Alloys: NiTiHf and NiTiZr

Ab initio simulations of phase stability and martensitic phase transitions are performed for NiTi-based ternary shape memory alloys (SMAs). Specifically, we considered NiTiHf and NiTiZr, which are highly studied for high temperature SMA applications. Previously, we performed investigations of ordered NiTi and related binaries [1,2]. However, similar approaches for chemically disordered compounds present additional difficulties. In this work, special quasi-random structures (SQS) were generated for various compositions, x∈[0,0.5], of Ni0.5Ti(0.5-x)Hfx and Ni0.5Ti(0.5-x)Zrx to capture chemical disorder of off-stoichiometric compounds. Phase stability was evaluated through analysis of finite temperature phonon spectra using temperature dependent effective potential (TDEP) method. Free energies for the cubic B2 phase of NiTiHf and NiTiZr were computed using ab initio thermodynamic integration (AITI) developed previously [1,2]. Free energies for monoclinic B19’ and orthorhombic B33 phases were evaluated via quasi harmonic approximations (QHA). Our results show a critical composition (xc) where the three phases of B2, B19’ and B33 meet, i.e. there is a tri-critical point. For x xc, the transition is between B33 and B2, i.e. it is not a shape memory transition. The approach presented here opens the door to ab initio based predictions of MTT for arbitrary ternary SMAs.

Hessam Malmir↗

Atomistic Modeling of Surface and Bulk Properties of Cu, Pd and the Cu-Pd System

The BFS (Bozzolo-Ferrante-Smith) method for alloys is applied to the study of the Cu-Pd system. A variety of issues are analyzed and discussed, including the properties of pure Cu or Pd crystals (surface energies, surface relaxations), Pd/Cu and Cu/Pd surface alloys, segregation of Pd (or Cu) in Cu (or Pd), concentration dependence of the lattice parameter of the high temperature fcc CuPd solid solution, the formation and properties of low temperature ordered phases, and order-disorder transition temperatures. Emphasis is made on the ability of the method to describe these properties on the basis of a minimum set of BFS universal parameters that uniquely characterize the Cu-Pd system.

Bozzolo, Guillermo↗

Structural stability, elemental ordering, and transport properties of layered ScTaN 2

Ternary transition metal (TM) nitrides have gained significant attention in thin film research due to their promising properties for a broad range of applications. Particularly, some of the ternary TM nitrides have been predicted to adopt layered structures that make them interesting for thermoelectric conversion and quantum materials applications. Unfortunately, synthesis of TM ternary nitride films by physical vapor deposition often favors disordered 3D structures rather than the predicted 2D-like layered structure. In this study, we investigate the structural interplay in the Sc-Ta-N ternary system using a combinatorial approach. Combinatorial libraries S⁢c 𝑥 ⁢T⁢a 1−𝑥 ⁢N are synthesized following a two-step method: First, deposit film precursors by cosputtering and then process the resulting 3D-structured samples with rapid thermal annealing. Synchrotron grazing-incidence wide-angle x-ray scattering on films annealed at 1200 ⁢°⁢C for 20 min leads to the nucleation of ScTaN 2 layered structure (𝑃⁢6 3 /𝑚⁢𝑚⁢𝑐) near stoichiometry. We find that the layered structure can accommodate large off-stoichiometry in the Ta-rich region (𝑥 < 0.5), facilitated by the alloying with quasi-isostructural Ta 5 ⁢N 6 compound that exists on a composition tie line at 𝑥 = 0. While focusing on ScTaN 2 , we estimate the long-range order parameter in near-stoichiometric films to be 0.86, corresponding to a fraction of Sc/Ta antisites of 7%. Transport measurements on ScTaN 2 reveal a nearly temperature-independent high carrier density (10 21 c⁢m −3 ), suggesting a heavily doped semiconductor or semimetallic character, consistent with a small positive Seebeck coefficient of +19 µV/K. The carrier mobility at 2 K is relatively small (9.5c⁢m 2 V −1 s −1 ) and the residual-resistivity ratio is minor, suggesting that electrical conduction is dominated by defects or disorder. Measured magnetoresistance suggests possible weak antilocalization at 2 K. This paper highlights the interplay between ScTaN 2 and Ta 5 ⁢N 6 crystal structures in stabilizing layered materials, emphasizes the importance of cation order/disorder for potential tunable alloys, and suggests that ScTaN 2 is a promising platform for exploring electronic properties.

36 MATERIALS SCIENCE↗

Advanced Colloids Experiment (ACE) Science Overview

The Advanced Colloids Experiment is being conducted on the International Space Station (ISS) using the Light Microscopy Module (LMM) in the Fluids Integrated Rack (FIR). Work to date will be discussed and future plans and opportunities will be highlighted. The LMM is a microscope facility designed to allow scientists to process, manipulate, and characterize colloidal samples in micro-gravity where the absence of gravitational settling and particle jamming enables scientists to study such things as:a.The role that disordered and ordered-packing of spheres play in the phase diagram and equation of state of hard sphere systems,b.crystal nucleation and growth, growth instabilities, and the glass transition, c.gelation and phase separation of colloid polymer mixtures,d.crystallization of colloidal binary alloys,e.competition between crystallization and phase separation,f.effects of anisotropy and specific interactions on packing, aggregation, frustration and crystallization,g.effects of specific reversible and irreversible interactions mediated in the first case by hybridization of complementary DNA strands attached to separate colloidal particles,h.Lock and key interactions between colloids with dimples and spheres which match the size and shape of the dimples,i.finding the phase diagrams of isotropic and interacting particles,j.new techniques for complex self-assembly including scenarios for self-replication, k.critical Casimir forces,l.biology (real and model systems) in microgravity,m.etc. By adding additional microscopy capabilities to the existing LMM, NASA will increase the tools available for scientists that fly experiments on the ISS enabling scientists to observe directly what is happening at the particle level. Presently, theories are needed to bridge the gap between what is being observed (at a macroscopic level when photographing samples) with what is happening at a particle (or microscopic) level. What is happening at a microscopic level will be directly accessible with the availability of the Light Microscopy Module (LMM) on ISS. To meet these goals, the ACE experiment is being built-up in stages, with the availability of confocal microscopy being the ultimate objective. Supported by NASAs Physical Sciences Research Program, ESAESTEC, and the authors respective governments.

Microgravity Biology Research↗

Doping with phosphorus reduces anion vacancy disorder in CdSeTe semiconductors enabling higher solar cell efficiency

Doping is used in many pn junction devices, such as polycrystalline solar cells, to increase the strength of the junction field to assist charge carrier collection and thus partially mitigate nonradiative recombination losses. We demonstrate a different doping characteristic for inorganic solar cells: using dopants to reduce charge carrier trapping and electronic band tails. Alloying CdTe with Se to form CdSeTe semiconductor reduced recombination, but CdSeTe has more complex defect states which can limit further efficiency gains due to charge carrier trapping and trap-limited mobility. Doping CdSeTe with P (but not N, As, or Sb in this study) reduces band tails (Urbach energies) and lessens the impact of the near valence band trap states, with ambipolar mobilities improving to >50 cm 2 V −1 s −1 , fill factor increasing from 76% to 79%, and efficiencies increasing by 0.9% absolute. Simulations are used to show how such defect reduction improves performance in the radiative limit.

14 SOLAR ENERGY↗

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗

Understanding how defects and dopant atoms in copper surface oxides affect reactivity

Copper and its oxides are key catalytic materials, on which reactions often occur at the metal/oxide interface. Here, in this work, we directly connect the induction period observed during methanol-driven reduction of thin-film copper oxides to their atomic-scale structural order. Using temperature-programmed desorption (TPD) methanol titrations combined with scanning tunneling microscopy, we show that highly ordered oxide phases – particularly the “29” structure with its low defect density – exhibit long induction periods and initially low reactivity. The induction period, defined as the number of methanol TPD cycles required to reach half of the maximum formaldehyde yield, scales with oxide order and oxygen coverage. Enhanced reactivity of well-ordered oxides emerges only after repeated methanol adsorption/desorption cycles generate oxygen vacancies and new Cu(111)/Cu x O interfacial sites. In contrast, disordered or sub-stoichiometric oxides, which contain more intrinsic defects and interfaces, are active from the first TPD cycle. We further examine how dilute Pt and Rh dopants influence oxide order and reactivity: 1% Pt increases defect density and catalytic activity, while 1% Rh promotes oxide ordering and longer induction periods. These findings demonstrate that dilute alloying provides a potential method for tuning the structure and reactivity of Cu(111)/Cu x O interfaces.

Cu(111)Methanol oxidation↗

Intermetallic phase formation in Al-Si-Zr alloys during hot isostatic pressing revealed by experiments and molecular dynamics

Understanding phase transformations at alloy interfaces is critical for the design of advanced structural materials. Here, in this study, we investigate the formation mechanisms of the Al 2 SiZr intermetallic phase in the Al-Si-Zr system under hot isostatic pressing (HIP) using molecular dynamics (MD) simulations and thermodynamic analysis. A unique aspect of our approach in MD involves the replacement of a disordered Al 2 SiZr stoichiometry with an ordered phase at the Al-Zr interface once HIP results in the desired Al 2 SiZr stoichiometry, allowing us to compute the total energetic cost of transformation by accounting for both formation energies and diffusion barriers. Diffusion coefficients and activation energies, extracted across a range of temperatures, reveal that HIP substantially enhances atomic mobility, creating favorable stoichiometry for phase evolution. Our results show that Al 2 SiZr phase formation is kinetically unfavorable at lower temperatures but becomes feasible when the thermodynamic driving energy surpass a critical energy threshold.

Roy, Ankit [Pacific Northwest National Laboratory ↗

Kinetics of amorphous defect phases measured through ultrafast nanocalorimetry

Recognition of the role of extended defects on local phase transitions has led to the conceptualization of the defect phase, localized thermodynamically stable interfacial states that have since been applied in a myriad of material systems to realize significant enhancements in material properties. Here, we explore the kinetics of grain boundary confined amorphous defect phases, utilizing the high temperature and scanning rates afforded by ultrafast differential scanning calorimetry to apply targeted annealing/quenching treatments at high rates capable of capturing the kinetic behavior. Four Al-based nanocrystalline alloys, including two binary systems, Al–Ni and Al–Y, and two ternary systems, Al–Mg–Y and Al–Ni–Y, are selected to probe the materials design space (enthalpy of mixing, enthalpy of segregation, chemical complexity) for amorphous defect phase formation and stability, with correlative transmission electron microscopy applied to link phase evolution and grain stability to nanocalorimetry signatures. A series of targeted isothermal annealing heat treatments is utilized to construct a Time–Temperature-Transformation curve for the Al–Ni system, from which a critical cooling rate of 2400 °C/s was determined for the grain boundary confined disordered-to-ordered transition. Finally, a thermal profile consisting of 1000 repeated annealing sequences was created to quantify the recovery of the amorphous defect phase following sequential annealing treatments, with results indicating remarkable microstructural stability after annealing at temperatures above 90% of the melting temperature. This work contributes to a deeper understanding of grain boundary localized thermodynamics and kinetics, with potential implications for the design and optimization of advanced materials with enhanced stability and performance.

Amorphous defect phases↗