M. S. Lucas

Absence of Long-Range Chemical Ordering in Equimolar FeCoCrNi

Equimolar FeCoCrNi alloys have been the topic of recent research as “high-entropy alloys,” where the name is derived from the high configurational entropy of mixing for a random solid solution. Despite their name, no systematic study of ordering in this alloy system has been performed to date. Here, we present results from anomalous x-ray scattering and neutron scattering on quenched and annealed samples. An alloy of FeNi3 was prepared in the same manner to act as a control. Evidence of long-range chemical ordering is clearly observed in the annealed FeNi3 sample from both experimental techniques. The FeCoCrNi sample given the same heat treatment lacks long-range chemical order.

Magnetic and Vibrational Properties of High-Entropy Alloys

The magnetic properties of high-entropy alloys based on equimolar FeCoCrNi were investigated using vibrating sample magnetometry to determine their usefulness in high-temperature magnetic applications. Nuclear resonant inelastic x-ray scattering measurements were performed to evaluate the vibrational entropy of the 57Fe atoms and to infer chemical order. The configurational and vibrational entropy of alloying are discussed as they apply to these high-entropy alloys.

Design and operation of the wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source

The wide angular-range chopper spectrometer ARCS at the Spallation Neutron Source (SNS) is optimized to provide a high neutron flux at the sample position with a large solid angle of detector coverage. The instrument incorporates modern neutron instrumentation, such as an elliptically focused neutron guide, high speed magnetic bearing choppers, and a massive array of (3)He linear position sensitive detectors. Novel features of the spectrometer include the use of a large gate valve between the sample and detector vacuum chambers and the placement of the detectors within the vacuum, both of which provide a window-free final flight path to minimize background scattering while allowing rapid changing of the sample and sample environment equipment. ARCS views the SNS decoupled ambient temperature water moderator, using neutrons with incident energy typically in the range from 15 to 1500 meV. This range, coupled with the large detector coverage, allows a wide variety of studies of excitations in condensed matter, such as lattice dynamics and magnetism, in both powder and single-crystal samples. Comparisons of early results to both analytical and Monte Carlo simulation of the instrument performance demonstrate that the instrument is operating as expected and its neutronic performance is understood. ARCS is currently in the SNS user program and continues to improve its scientific productivity by incorporating new instrumentation to increase the range of science covered and improve its effectiveness in data collection.

Phonon softening and metallization of a narrow-gap semiconductor by thermal disorder

The vibrations of ions in solids at finite temperature depend on interatomic force–constants that result from electrostatic interactions between ions, and the response of the electron density to atomic displacements. At high temperatures, vibration amplitudes are substantial, and electronic states are affected, thus modifying the screening properties of the electron density. By combining inelastic neutron scattering measurements of Fe1-xCoxSi as a function of temperature, and finite-temperature first-principles calculations including thermal disorder effects, we show that the coupling between phonons and electronic structure results in an anomalous temperature dependence of phonons. The strong concomitant renormalization of the electronic structure induces the semiconductor-to-metal transition that occurs with increasing temperature in FeSi. Our results show that for systems with rapidly changing electronic densities of states at the Fermi level, there are likely to be significant phonon–electron interactions, resulting in anomalous temperature-dependent properties.

Thermomagnetic analysis of FeCoCrxNi alloys: Magnetic entropy of high-entropy alloys

The equimolar alloy FeCoCrNi, a high-entropy alloy, forms in the face-centered-cubic crystal structure and has a ferromagnetic Curie temperature of 130 K. In this study, we explore the effects of Cr concentration, cold-rolling, and subsequent heat treatments on the magnetic properties of FeCoCrxNi alloys. Cr reductions result in an increase of the Curie temperature, and may be used to tune the TC over a very large temperature range. The magnetic entropy change for a change in applied field of 2T is ΔSm = −0.35 J/(kg K) for cold-rolled FeCoCrNi. Cold-rolling results in a broadening of ΔSm, where subsequent heat treatment at 1073 K sharpens the magnetic entropy curve. In all of the alloys, we find that upon heating (after cold-rolling) there is a re-entrant magnetic moment near 730 K. This feature is much less pronounced in the as-cast samples (without cold-rolling) and in the Cr-rich samples, and is no longer observed after annealing at 1073 K. Possible origins of this behavior are discussed.

“Treasure maps” for magnetic high-entropy-alloys from theory and experiment

The critical temperature and saturation magnetization for four- and five-component FCC transition metal alloys are predicted using a formalism that combines density functional theory and a magnetic mean-field model. Our theoretical results are in excellent agreement with experimental data presented in both this work and in the literature. The generality and power of this approach allow us to computationally design alloys with well-defined magnetic properties. Among other alloys, the method is applied to CoCrFeNiPd alloys, which have attracted attention recently for potential magnetic applications. The computational framework is able to predict the experimentally measured TC and to explore the dominant mechanisms for alloying trends with Pd. A wide range of ferromagnetic properties and Curie temperatures near room temperature in hitherto unexplored alloys is predicted in which Pd is replaced in varying degrees by, e.g., Ag, Au, and Cu.

Tunable magnetocaloric effect in transition metal alloys.

The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

Effects of chemical composition and B2 order on phonons in bcc Fe–Co alloys

The phonon density of states (DOS) gives insight into interatomic forces and provides the vibrational entropy, making it a key thermodynamic function for understanding alloy phase transformations. Nuclear resonant inelastic x-ray scattering and inelastic neutron scattering were used to measure the chemical dependence of the DOS of bcc Fe–Co alloys. For the equiatomic alloy, the A2→B2 (chemically disordered→chemically ordered) phase transformation caused measurable changes in the phonon spectrum. The measured change in vibrational entropy upon ordering was −0.02±0.02 k_B/atom, suggesting that vibrational entropy results in a reduction in the order–disorder transition temperature by 60±60 K. The Connolly–Williams cluster inversion method was used to obtain interaction DOS (IDOS) curves that show how point and pair variables altered the phonon DOS of disordered bcc Fe–Co alloys. These IDOS curves accurately captured the change in the phonon DOS and vibrational entropy of the B2 ordering transition.

Effect of surfactant molecular weight on particle morphology of SmCo5 prepared by high energy ball milling

Surfactant-assisted high energy ball milling (HEBM) is a widely used technique for producing nanostructured magnetic materials with oleic acid (OA) being the most commonly utilized surfactant reported in literature to date. No conclusive explanation has been presented for the wide use of OA and only a few studies have deviated from its use. OA has a boiling point of 360 °C which presents issues for complete removal of the surfactant after the HEBM process. Exposing the nanostructured materials to the high temperatures required for surfactant removal is known to result in grain growth and oxidation. In other studies, select surfactant systems, such as octanoic acid or oleylamine, have been used, however, a systematic study examining the dependence of surfactant selection on overall particle (flake) morphology has yet to be performed. In this study, we have qualitatively and quantitatively examined the effects of surfactant selection on the morphology and magnetic properties of SmCo5 utilizing surfactants with lower boiling points that are structurally similar to OA. Our results demonstrate that there was little change in the morphological and magnetic properties for the different surfactants. The implication is that lower boiling point surfactants may be used for HEBM, which require less severe conditions for surfactant removal after milling thereby preserving the integrity of the powders.

Effect of milling time on magnetic properties and structures of bulk Sm-Co/α-(Fe, Co) nanocomposite magnets

Bulk Sm-Co/α-(Fe,Co) nanocomposite magnets were fabricated by hot pressing composite powders prepared by high-energy ball milling of magnetically hard SmCo5 powder and magnetically soft Fe powder. The bulk magnets had a nanocomposite structure consisting of Sm-Co matrix (1:5 H and 1:7 H phases) and α-(Fe,Co) phases. The Fe-Co particles were distributed uniformly in the Sm-Co matrix. The milling time strongly affects the structures and the magnetic properties of the bulk magnets. Increasing milling time led to a decrease of the amount of 1:5 H phase, an increase in the phase fraction of the 1:7 H phase, and a decrease in the amount of soft phase, which resulted in an increase in magnetization and a decrease in coercivity. Scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS) analyses revealed that inter-diffusion took place between the Sm-Co matrix and Fe particles during the processing.