skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Effects of doping, hydrostatic pressure, and thermal quenching on the phase transitions and magnetocaloric properties in Mn1− x Co x NiGe
The effects of doping, hydrostatic pressure, and thermal quenching on the phase transitions and magnetocaloric properties of the Mn1−xCoxNiGe system have been investigated. Cobalt doping on the Mn site shifted the martensitic structural transition toward lower temperature until it was ultimately absent, leaving only a magnetic transition from a ferromagnetic (FM) to a paramagnetic (PM) state in the high-temperature hexagonal phase. Co-occurrence of the magnetic and structural transitions to form a first-order magnetostructural transition (MST) from the FM orthorhombic to the PM hexagonal phase was observed in samples with 0.05 < x < 0.20. An additional antiferromagnetic–ferromagnetic-like transition was observed in the martensite phase for 0.05 < x < 0.10, which gradually vanished with increasing Co concentration (x > 0.10) or magnetic field (H > 0.5 T). The application of external hydrostatic pressure shifted the structural transition to lower temperature until an MST was formed in samples with x = 0.03 and 0.05, inducing large magnetic entropy changes up to −80.3 J kg−1 K−1 (x = 0.03) for a 7-T field change under 10.6-kbar pressure. Similar to the effects of the application of hydrostatic pressure, an MST was formed near room temperature in the sample with x = 0.03 by annealing at high temperature (1200 °C) followed by quenching, resulting in a large magnetic entropy change of −56.2 J kg−1 K−1. These experimental results show that the application of pressure and thermal quenching, in addition to compositional variations, are effective methods to create magnetostructural transitions in the MnNiGe system, resulting in large magnetocaloric effects.  more » « less
Award ID(s):
1904636
PAR ID:
10562110
Author(s) / Creator(s):
; ; ; ; ; ; ;
Publisher / Repository:
AIP Publishing
Date Published:
Journal Name:
Journal of Applied Physics
Volume:
132
Issue:
4
ISSN:
0021-8979
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Metastable phases were formed in Mn1−xCoxNiGe (x=0.05 and 0.08) by annealing at 800 °C followed by rapid cooling, i.e., quenching, at ambient pressure (P=0) and under a pressure of P=3.5 GPa, and their phase transitions and associated magnetocaloric properties were investigated. The crystal cell volumes of the metastable phases decreased, and their structural transitions significantly shifted to lower temperatures relative to those of the slow-cooled compounds, with a greater reduction observed in the samples where the rapid cooling occurred under high pressures. The magnetic and structural transitions coupled to form a magnetostructural transition in the metastable phases, resulting in large magnetic entropy changes up to −79.6 J kg−1 K−1 (x=0.08) for a 7-T field change. The experimental results demonstrate thermal quenching and high-pressure annealing as alternative methods to create magnetostructural transitions, without modifying the compositions of the materials. 
    more » « less
  2. In this study, phase transitions (structural and magnetic) and associated magnetocaloric properties of stoichiometric MnCoGe have been investigated as a function of annealing pressure. Metastable phases were generated by annealing at 800 °C followed by rapid cooling under pressures up to 6.0 GPa. The x-ray diffraction results reveal that the crystal cell volume of the metastable phases continuously decreases with increasing thermal processing pressure, leading to a decrease in the structural transition temperature. The magnetic and structural transitions merge and form a first-order magnetostructural transition between the ferromagnetic orthorhombic and paramagnetic hexagonal phases over a broad temperature range (>80 K) spanning room temperature, yielding considerable magnetic entropy changes. These findings demonstrate the utility of thermal processing under high pressure, i.e., high-pressure annealing, to control the magnetostructural transitions and associated magnetocaloric properties of MnCoGe without altering its chemical composition. 
    more » « less
  3. Abstract The phase transitions in MnNiGe compounds were explored by manipulating the heat treatment conditions and through hydrostatic pressure application. As the quenching temperature increased, both the first-order martensitic structural transition temperatures and magnetic transition temperatures decreased relative to those in the slowly-cooled samples. When the samples were quenched from 1200 C, the first-order martensitic structural transition temperature lowered by more than 200 K. The structural transitions also shifted to lower temperature with the application of hydrostatic pressure during measurement. Temperature-dependent x-ray diffraction results reveal that the changes of the cell parameters resulting from the structural transitions are nearly identical for all samples regardless of the extensive variation in their structural transition temperatures. In addition, neutron scattering measurements confirm the magnetic structure transition between simple and cycloidal spiral magnetic structures. 
    more » « less
  4. MnCoGe-based materials have the potential to exhibit giant magnetocaloric effects due to coupling between magnetic ordering and a martensitic phase transition. Such coupling can be realized by matching the temperatures of the magnetic and structural phase transitions. To understand the site preference of different elements and the effect of hole or electron doping on the stability of different polymorphs of MnCoGe, crystal orbital Hamilton population (COHP) analysis has been employed for the first time to evaluate peculiarities of chemical bonding in this material. The shortest Mn–Mn bond in the structure is found to be pivotal to the observed ferromagnetic behavior and structural stability of hexagonal MnCoGe. Based on this insight, eliminating anti-bonding features of the shortest Mn-Mn bond at the Fermi energy is proposed as a feasible way to stabilize the hexagonal polymorph, which is then realized experimentally by substitution of Zn for Ge. The hexagonal MnCoGe structure is stabilized due to depopulation of the anti-bonding states and strengthening of the Mn–Mn bonding. This change in chemical bonding leads to anisotropic evolution of lattice parameters. The structural and magnetic properties of Zn-doped MnCoGe have been elucidated by synchrotron X-ray diffraction and magnetic measurements, respectively. 
    more » « less
  5. Promising materials for magnetic refrigeration and thermomagnetic power generation often display strong coupling between magnetism and structure. It has been previously proposed that MnCoP exhibits this strong coupling, contributing to its substantial magnetocaloric effect near TC = 578K. Here, we show from temperature-dependent synchrotron x-ray diffraction that MnCoP displays a discontinuity in the thermal expansion at TC, with spontaneous magnetostriction that is positive in the a direction and negative in the b direction, highlighting the anisotropic nature of the magnetostructural coupling. Varying the Mn:Co ratio of Mn2−xCoxP within the range of 0.6 ≤ x ≤ 1.4 allows the magnetic properties to be tuned. TC decreases as the composition deviates from stoichiometric MnCoP, as does the saturation magnetization. The magnitude of the magnetocaloric effect, |ΔSM|, decreases as well, due to broadening of the magnetic transition. The large reversible change in magnetization ΔM accessible over a small temperature range under moderate magnetic fields makes these materials promising for thermomagnetic power generation from waste heat. 
    more » « less