Ni-Mn-In magnetic shape-memory Heusler alloys exhibit generally a large thermal hysteresis at their first-order martensitic phase transition which hinder a technological application in magnetic refrigeration. By optimizing the Cu content in Ni$_2$Cu$_x$Mn$_{1.4-x}$In$_{0.6}$, we obtained a thermal hysteresis of the martensitic phase transition in Ni$_{2}$Cu$_{0.2}$Mn$_{1.2}$In$_{0.6}$ of only 6 K. We can explain this very small hysteresis by an almost perfect habit plane at the interface of martensite and austenite phases. Application of hydrostatic pressure does not reduce the hysteresis further, but shifts the martensitic transition close to room temperature. The isothermal entropy change does not depend on warming or cooling protocols and is pressure independent. Experiments in pulsed-magnetic fields on Ni$_{2}$Cu$_{0.2}$Mn$_{1.2}$In$_{0.6}$ find a reversible magnetocaloric effect with a maximum adiabatic temperature change of -13 K.
Polycrystalline Ni2.18Mn0.82Ga Heusler alloys with a coupled magnetostructural transition are studied by differential scanning calorimetry, magnetic and resistivity measurements. Coupling of the magnetic and structural subsystems results in unusual magnetic features of the alloy. These uncommon magnetic properties of Ni2.18Mn0.82Ga are attributed to the first-order structural transition from a tetragonal ferromagnetic to a cubic paramagnetic phase.
The magnetic and thermodynamic properties of a Ni2.19Mn0.81Ga alloy with coupled magnetic and structural (martensitic) phase transitions were studied experimentally and theoretically. The magnetocaloric effect was measured by a direct method in magnetic fields 0-26 kOe at temperatures close to the magnetostructural transition temperature. For theoretical description of the alloy properties near the magnetostructural transition a statistical model is suggested, that takes into account the coexistence of martensite and austenite domains in the vicinity of martensite transformation point.
The all-d-metal Mn2-based Heusler ferromagnetic shape memory alloys Mn50Ni40-xCoxTi10 (x = 8 and 9.5) are realized. With a generic comparison between d-metal Ti and main-group elements in lowering the transformation temperature, the magnetostructural martensitic transformations are established by further introducing Co to produce local ferromagnetic Mn-Co-Mn configurations. A 5-fold modulation and (3, -2) stacking of [00 10] of martensite are determined by XRD and HRTEM analysis. Based on the transformation, a large magneto-strain of 6900 ppm and a large volume change of -2.54% are observed in…
We report an improved reversibility of magnetostriction and inverse magnetocaloric effect (MCE) for the magnetic shape-memory Heusler alloy Ni$_{1.8}$Mn$_{1.8}$In$_{0.4}$. We show that the magnetostriction and MCE crucially depends on the geometrical compatibility of the austenite and martensite phases. Detailed information on the compatibility of both phases has been obtained from the transformation matrix calculated from x-ray diffraction data. The uniqueness of the lattice parameters results in an improved reversibility of the magnetostriction and the MCE. In the thermal hysteresis region o…
Structural and magnetic properties of the CoMn$_{0.88}$Cu$_{0.12}$Ge compound have been investigated using X-ray diffraction (XRD) and differential scanning calorimetry (DSC) accompanied with investigation of magnetic properties under applied hydrostatic pressure up to 12 kbar. It has been found that the orthorhombic crystal structure of the TiNiSi-type, which is dominant at low temperatures, turns into the hexagonal Ni$_2$In-type one, slightly above 200 K. The structural transition is of the first-order type as confirmed by presence of distinct thermal hysteresis exceeding 20 K. The ac magnet…
The large magnetocaloric effect (MCE) observed in Ni-Mn based shape-memory Heusler alloys put them forward to use in magnetic refrigeration technology. It is associated with a first-order magnetostructural (martensitic) phase transition. We conducted a comprehensive study of the MCE for the off-stoichiometric Heusler alloy Ni$_{2.2}$Mn$_{0.8}$Ga in the vicinity of its first-order magnetostructural phase transition. We found a reversible MCE under repeated magnetic field cycles. The reversible behavior can be attributed to the small thermal hysteresis of the martensitic phase transition. Based …
We report the effect of hydrostatic pressure on the magnetic and structural properties of the shape-memory Heusler alloy Ni50Mn35In15. Magnetization and x-ray diffraction experiments were performed at hydrostatic pressures up to 5 GPa using diamond anvil cells. Pressure stabilizes the martensitic phase, shifting the martensitic transition to higher temperatures and suppresses the ferromagnetic austenitic phase. Above ~3 GPa, where the martensitic-transition temperature approaches the Curie temperature in the austenite, the magnetization shows no indication of ferromagnetic ordering anymore. We…
The isostructural alloying of two compounds with extremely different magnetic and thermo-structural properties has resulted in a new system, (MnNiSi)1-x(FeCoGe)x, that exhibits extraordinary magnetocaloric properties with an acute sensitivity to applied hydrostatic pressure (P). Application of hydrostatic pressure shifts the first-order phase transition to lower temperature ($Δ$ T=-41 K with P=3.43 kbar) but preserves the giant value of isothermal entropy change (-$Δ$S$\max$=143.7 J/kg K for a field change of ΔB=5 T at atmospheric pressure). Together with the magnetic field, this pressure-indu…
A systematic study of magnetic properties of Ni2+xMn1-xGa (0 \le x \le 0.19) Heusler alloys undergoing structural martensite-austenite transformations while in ferromagnetic state has been performed. From measurements of spontaneous magnetization, Ms(T), jumps ΔM at structural phase transitions were determined. Virtual Curie temperatures of the martensite were estimated from the comparison of magnetization in martensitic and austenitic phases. Both saturation magnetic moments in ferromagnetic state and effective magnetic moments in paramagnetic state of Mn and Ni atoms were estimated and the i…
Polycrystalline Heusler compounds Ni2Mn0.75Cu0.25Ga0.84Al0.16 with a martensitic transition between ferromagnetic phases and Ni2Mn0.70Cu0.30Ga0.84Al0.16 with a magnetostructural transformation were investigated by magnetization and thermal measurements, both as a function of temperature and magnetic field. The compound Ni2Mn0.75Cu0.25Ga0.84Al0.16 presents a large magnetocaloric effect among magnetically aligned structures and its causes are explored. In addition, Ni2Mn0.70Cu0.30Ga0.84Al0.16 shows very high, although irreversible, entropy and adiabatic temperature change at room temperature und…
The hydrostatic pressure is expected to be an effective knob to tune the magnetostructural phase transitions of hexagonal MMX alloy. In this study, magnetization measurements under hydrostatic pressure were performed on a MMX martensitic MnNi0.77Fe0.23Ge alloy. The magnetostructural transition temperature can be efficiently tuned to lower temperatures by applying moderate pressures, with a giant shift rate of -151 K GPa-1. A temperature span of 30 K is obtained under the pressure, within which a large magnetic entropy change of -23 J kg-1 K-1 in a field change of 5 T is induced by the mechanic…
The structural and magnetic properties of functional Ni-Mn-Z (Z = Ga, In, Sn) Heusler alloys are studied by first-principles and Monte Carlo methods. The \textit{ab initio} calculations give a basic understanding of the underlying physics which is associated with the strong competition of ferro- and antiferromagnetic interactions with increasing chemical disorder. The resulting $d$-electron orbital dependent magnetic ordering is the driving mechanism of magnetostructural instability which is accompanied by a drop of magnetization governing the size of the magnetocaloric effect. The thermodynam…
Heusler alloys are promising for several applications, including magnetic refrigeration, due to high magnetocaloric and magnetovolume effects. One way to optimize this potential is by increasing the magnetovolume effect. Using density functional theory with the Korringa-Kohn-Rostoker method, we calculate the effective exchange interaction energies and corresponding mean field Curie temperature as a function of the volume (hydrostatic pressure) in several L2 1 -type Co 2 YZ Heusler alloys. Different qualitative trends and signs of the pressure derivatives of the Curie temperature and moments ar…
The structural and magnetic properties of transition metal-doped Mn$_3$SnC are studied with an aim to understand the effect of transition metal atom on magnetostructural properties of the antiperovskite compound. The doped Mn$_{2.8}$T$_{0.2}$SnC (T = Cr, Fe, Co, Ni and Cu) compounds show a distinctly different magnetic behavior which can be related to electronic filling of the $d$ band of the transition metal atom. While Cr and Fe doped Mn$_3$SnC show properties similar to that of Mn$_3$SnC, the Co, Ni and Cu doped compounds exhibit nucleation of secondary phases which are devoid of carbon and…
Polycrystalline samples of Co$_{1-x}$Cu$_x$MnGe ($x=0.05, 0.10, 0.15, 0.22$ and 0.35), prepared by arc melting under argon atmosphere, have been annealed at 1123 K with final furnace cooling. The samples have been investigated by powder X-ray diffraction (in function of temperature) and ac magnetic measurements (in function of temperature and applied hydrostatic pressure up to 12 kbar). On the basis of the experimental data, the $(p,T)$ phase diagrams have been determined. For the low Cu content ($x=0.05$, 0.10 and 0.15), the compounds show a martensitic transition between the low-temperature …
A remarkable decrease of the structural transition temperature of MnNiSi from 1200 K to <300 K by chemically alloying it with MnFeGe results in a coupling of the magnetic and structural transitions, leading to a large magnetocaloric effect near room temperature. It was found that the magnetostructural transition is highly sensitive to external (hydrostatic) pressure: relatively low hydrostatic pressures (~2.4 kbar) lead to an extraordinary enhancement of the isothermal entropy change from $-$Δ$S$ = 44 to 89 J/kg K at ambient (atmospheric) and 2.4 kbar applied pressures, respectively, for a fie…
Novel Ni-Co-Mn-Ti all-d-metal Heusler alloys are exciting due to large multicaloric effects combined with enhanced mechanical properties. An optimized heat treatment for a series of these compounds leads to very sharp phase transitions in bulk alloys with isothermal entropy changes of up to 38 J kg$^{-1}$ K$^{-1}$ for a magnetic field change of 2 T. The differences of as-cast and annealed samples are analyzed by investigating microstructure and phase transitions in detail by optical microscopy. We identify different grain structures as well as stoichiometric (in)homogenieties as reasons for di…
The large magnetocaloric effect in Heusler alloys showing martensite phase transformation puts them forward as efficient materials for magnetic refrigeration. However, irreversibility of the magnetocaloric cooling cycle is a major challenge for real applications. This irreversibility is directly linked to the thermal hysteresis at the first-order martensite phase transition. Therefore, minimizing the hysteresis is essential in order to achieve reversibility. Here we show a large reduction in the thermal hysteresis at the martensite transition in the Ni$_{2}$Mn$_{1.4}$In$_{0.6}$ and Ni$_{1.8}$C…
Heusler compounds offer potential as spintronic devices due to their spin-polarization and half-metallicity properties, where electron spin-majority (minority) manifold exhibits states (band gap) at the electronic chemical potential, yielding full spin-polarization in a single manifold. Yet, Heuslers often exhibit intrinsic disorder that degrades its half-metallicity and spin-polarization. Using density-functional theory, we analyze the electronic and magnetic properties of equiatomic Heusler ($L$2$_{1}$) CoMnCrAl and CoFeCrGe alloys for effects of hydrostatic pressure and intrinsic disorder (…
We propose the phase diagram of a new pseudo-ternary compound, CoMnGe_{1-x}Sn_{x}, in the range x less than or equal to 0.1. Our phase diagram is a result of magnetic and calometric measurements. We demonstrate the appearance of a hysteretic magnetostructural phase transition in the range x=0.04 to x=0.055, similar to that observed in CoMnGe under hydrostatic pressure. From magnetisation measurements, we show that the isothermal entropy change associated with the magnetostructural transition can be as high as 4.5 J/(K kg) in a field of 1 Tesla. However, the large thermal hysteresis in this tra…
In this work, we present structural, electronic, magnetic, mechanical and transport properties of equiatomic quaternary Heusler alloy, CoRhMnGe using both theoretical and experimental techniques. A detailed structural analysis is performed using X-ray diffraction(XRD) and extended X-ray absorption fine structure(EXAFS) spectroscopy. The alloy is found to crystallize in Y-type structure having space group $F\bar{4}3m$ (\# 216). The ab-initio simulation pedict half-metallic ferromagnetic characteristics leading to large spin polarization. The calculated magnetization is found to be in fair agree…
The inverse magnetocaloric effect (MCE) in Ni-Mn-based Heusler compounds occurs during the magnetostructural transition between low-temperature, low-magnetization martensite and high-temperature, high-magnetization austenite. In this study, we analyze the metamagnetic transformation of a $Ni_{49.8}Mn_{35}In_{15.2}$ compound by simultaneous adiabatic temperature change and strain measurements in pulsed magnetic fields up to 10 T. We observe an adiabatic temperature change of -10 K and a strain of -0.22 % when the reverse martensitic transition is fully induced at a starting temperature of 285 K…
XX'YZ equiatomic quaternary Heusler alloys (EQHA's) containing Cr, Al, and select Group IVB elements ($\textit{M}$ = Ti, Zr, Hf) and Group VB elements ($\textit{N}$ = V, Nb, Ta) were studied using state-of-the-art density functional theory to determine their effectiveness in spintronic applications. Each alloy is classified based on their spin-dependent electronic structure as a half-metal, a spin gapless semiconductor, or a spin filter material. We predict several new fully-compensated ferrimagnetic spin filter materials with small electronic gaps and large exchange splitting allowing for rob…
Ni-Mn-based Heusler alloys, in particular all-d-metal Ni(-Co)-Mn-Ti, are highly promising materials for energy-efficient solid-state refrigeration as large multicaloric effects can be achieved across their magnetostructural martensitic transformation. However, no comprehensive study on the crucially important transition entropy change $Δs_t$ exists so far for Ni(-Co)-Mn-Ti. Here, we present a systematic study analyzing the composition and temperature dependence of $Δs_t$. Our results reveal a substantial structural entropy change contribution of approximately 65 J(kgK)$^{-1}$, which is compens…
Using first-principles electronic structure calculations, we have studied the dependence of the Curie temperature on external hydrostatic pressure for random Ni2MnSn Heusler alloys doped with Cu and Pd atoms, over the entire range of dopant concentrations. The Curie temperatures are calculated by applying random-phase approximation to the Heisenberg Hamiltonian whose parameters are determined using the linear response and multiple scattering methods, based on density-functional theory. In (Ni1-x,Pdx)2MnSn alloys, the Curie temperature is found to increase with applied pressure over the whole c…
Novel multicaloric cooling utilizing the giant caloric response of Ni-Mn-based metamagnetic shape-memory alloys to different external stimuli such as magnetic field, uniaxial stress and hydrostatic pressure is a promising candidate for energy-efficient and environmentally-friendly refrigeration. However, the role of microstructure when several external fields are applied simultaneously or sequentially has been scarcely discussed in literature. Here, we synthesized ternary Ni-Mn-In alloys by suction casting and arc melting and analyzed the microstructural influence on the response to magnetic f…
Caloric responses (temperature changes) can be induced in solid-state materials by applying external stimuli such as stress, pressure, and electric and magnetic fields. The magnetic-field-stimulated response is called the magnetocaloric effect, and materials that exhibit this property have long been sought for applications in room temperature magnetic cooling due to their potentially superior efficiency and low impact on the environment. Other solid-state caloric phenomena are less developed, but are likewise under intense investigation. Here we introduce a new material that not only displays …
High-quality single crystals of CoTiO$_3$ are grown and used to elucidate in detail structural and magnetostructural effects by means of high-resolution capacitance dilatometry studies in fields up to 15 T which are complemented by specific heat and magnetization measurements. In addition, we refine the single-crystal structure of the ilmenite ($R\bar{3}$) phase. At the antiferromagnetic ordering temperature $T_\mathrm{N}$, pronounced $λ$-shaped anomaly in the thermal expansion coefficients signals shrinking of both the $c$ and $b$ axes, indicating strong magnetoelastic coupling with uniaxial …
