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 57 Fe atoms and to infer chemical order. The configurational and vibrational entropy of alloying are discussed as they apply to these high-entropy alloys.
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 FeNi 3 was prepared in the same manner to act as a control. High-entropy alloys (HEAs) are multicomponent alloys where the atomic fraction of each of the elements is nearly equal.~ These materials have been studied for their high hardness, resistance to wear, and corrosion resistance. Wang et al. showed that ordered NiAl forms in the alloy FeCoCrNiA1Cu,2 whichwas cited as the main cause for strengthening in the alloy. Indeed, superlattice reflections indicative of chemical ordering have been observed in the x-ray diffraction (XRD) patterns presented in several studies.
Phonon density of states (DOS) curves were measured on alloys of face-centered-cubic (fcc) Au-Fe using nuclear resonant inelastic x-ray scattering (NRIXS) and inelastic neutron scattering (INS). The NRIXS and INS results were combined to obtain the total phonon DOS and the partial phonon DOS curves of Au and Fe atoms, from which vibrational entropies were calculated. The main effect on the vibrational entropy of alloying comes from a stiffening of the Au partial phonon DOS with Fe concentration. Force constants were calculated from first principles for several compositions and show a local stiffening of Au-Au bonds close to Fe atoms. The calculated phonon DOS curves reproduce the experimental trend. The stiffening is attributed to two main effects comparable in magnitude: 1) an increase in electron density in the free-electron-like states, and 2) stronger sd-hybridization.
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.
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.
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