Next Article in Journal
Microstructure Evolution and Precipitation Behavior in Nb and Nb-Mo Microalloyed Fire-Resistant Steels
Previous Article in Journal
Scattering Behavior of Slivers in Shearing of Magnetized Ultra-High-Strength Steel Sheets
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Metals
Volume 13
Issue 1
10.3390/met13010111
metals-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

All-d-Metal Heusler Alloys: A Review

by
Tarek Bachagha
1,2,* and
Joan-Josep Suñol
2,*
1
Physics Department, International Center of Quantum and Molecular Structures, Shanghai University, Shanghai 200444, China
2
Physics Department, Campus Montilivi s/n, Universitat de Girona, 17071 Girona, Spain
*
Authors to whom correspondence should be addressed.
Metals 2023, 13(1), 111; https://doi.org/10.3390/met13010111
Submission received: 23 November 2022 / Revised: 19 December 2022 / Accepted: 29 December 2022 / Published: 5 January 2023
(This article belongs to the Section Crystallography and Applications of Metallic Materials)
Browse Figures
Versions Notes

Abstract

:
Heusler alloy research has increased considerably in recent years. This is mostly due to their strong desire to develop future smart device applications. However, many limiting variables remain for researchers to overcome in order to enhance their functional properties. The poor mechanical properties of these alloys restrict their use as solid-state cooling materials in magnetic refrigeration devices. A promising strategy, resulting in novel compounds with better mechanical properties and substantial magnetocaloric effects, is favoring the d–d hybridization with transition-metal elements to replace p–d hybridization. The term given to these materials is “all-d-metal”. In light of recent experimental results of the magnetocaloric effect and the increased mechanical characteristics in these alloys (with complex crystallographic behavior due to off-stoichiometry and disorder), a review of this advanced functional behavior is offered. Moreover, the impact of the substitution of transition metal for the p-group to increase mechanical ductility and considerable magnetocaloric effects has also been addressed. These Heusler alloys are a potential new class of materials for technological applications because of their optimum functional behavior. Finally, we highlighted the potential challenges and unsolved issues in order to guide future studies on this topic.

1. Introduction

Most research funding organizations across the globe prioritize energy efficiency and sustainability, and these issues are often discussed in the media. According to statistics from the Lawrence Livermore National Laboratory, the expected US energy consumption until 2021 corresponds to rejected energy was to be 61%, while only 39% was used in energy services. Other developed countries have similar statistics, such as the United Kingdom and Spain, where 63% rejected energy was detected in 2011. These findings demonstrate the need to focus on the primary energy source and avoid dependency on non-renewable energy sources, as well as devoting major research resources to improving energy conversion efficiency. Most renewable energy sources must be converted, in particular, into electricity before being used, with 67% of the conversion process resulting in lost energy in the United States in 2015 [1]. In many cases, magnetic materials play a vital role in the conversion of energy into electricity. This is a driving force behind the development of magnetic materials for energy applications [2]. Air conditioning and refrigeration consume a significant amount of electricity in both the residential and industrial sectors, with quantities varying from country to country due to climatic differences. In fact, specific effects appear when ferromagnetic shape memory alloys (FSMAs) are subjected to external magnetic fields (magnetocaloric (MCE)), hydrostatic pressure (barocaloric (BCE)), and uniaxial stress (elastocaloric (eCE)), this technology is dependent on thermal processes [3,4,5,6,7]. Due to its important role in improving refrigeration system functionality, exploring good materials based on caloric impacts has progressively grown to be a hot research topic. The exceptional multi-magnetofunctional features of Ni−Mn-based Heusler alloys, connected to their tightly coupled ferromagnetic (FM) martensitic transition (MT) around transition temperature (Tt), have received growing interest. Moreover, Ni−Mn-based alloys generally display the first-order phase transition (FOPT) related to the magnetic transition because of the strong coupling between lattice structure transition and magnetism [8]. Furthermore, a significant MCE is caused by a rapid shift in magnetization from a weak-magnetic to a ferromagnetic (FM) state when the magnetic field is applied or removed. Therefore, during MT and under uniaxial stress, the eCE would be created by the FOPT. Due to the coexistence of MCE and eCE, these alloys are being evaluated as potential prospects for industrial uses. The Ni–Mn–Ga [9], Ni–Mn–Ga–Co [10], Co–Ni–Al [11], Ni–Mn–Sn–Cu [12], and Ni–Co–Mn–Sn [13] shape memory alloys have been examined as exhibit both properties. Because of their excellent magnetic properties and tunable MT temperatures, Ni–Mn-based alloys have been regarded as improved alloys among these noted [14]. In addition, the brittleness of most of these alloys restricts their applications and causes cracking under repetitive stress cycling [15]. Moreover, to reduce the hysteresis behavior associated with MT and improve the mechanical performance, several methods, such as introducing a second phase into grain boundaries, alloying with additional elements, and micro-alloying with boron, are proposed [16,17,18]. However, the covalent character of this orbital has recently been linked to the poor mechanical performance of Heusler alloys, a disadvantage that limits practical use [19]. Due to their mechanical response, Heusler alloys’ useful life as cooling materials and/or mechanical actuators is reduced, which causes structural fatigue when subjected to repeated thermo-mechanical/magnetic cycles. It is well-known that intrinsic brittleness is one of the largest and most pressing concerns to be solved in terms of appropriateness for technology applications [20].
Several approaches have been employed to restrict the macroscopic effects of the intrinsic brittle nature of these alloys, as briefly discussed in reference [21]. However, significant findings of a distinct class of Heusler alloys generated by substituting the p-group atom with a third transition metal, i.e., alloys made entirely of transition metal elements, have been found in recent years. In these alloys, considerable p–d hybridization among the elements is replaced by d–d hybridization, resulting in increased mechanical properties [19,22] associated with the MT and intense MCEs.
This review examines the basic and functional features of full Heusler alloys, with a particular focus on the impact of p–d orbital hybridization. Following that, we discuss the basic and functional features of all-d-metal Heusler alloys, with a focus on the effect of d–d orbital hybridization. Then, we examine some of the most current research on these unique families. Finally, we provide an outlook on the issue, as well as some perspectives for future research.

2. Heusler Alloys

2.1. Composition

Heusler alloys are magnetic intermetallic with face-centered cubic structure and composition of XYZ (half-Heusler) or X2YZ (full-Heusler), where X and Y are transition metals, and Z is in the p-group [23]. In a few cases, the Y atom can be replaced by alkaline earth metal or rare earth (lanthanide family) [24]. In the molecular formula, the transition metal element with the most atoms is placed first, followed by the p-group atom.

2.2. Crystalline Structure

Full Heusler alloys crystallize in a face-centered cubic structure that belongs to the Fm3m space group and includes Cu2MnAl as the prototype structure at room temperature (RT). This crystallographic structure is referred known as L21. Heusler alloys X2YZ typically have an ordered cubic structure. The four Wyckoff positions in the lattice are A (0, 0, 0), B (¼, ¼, ¼), C (½, ½, ½), and D (¾, ¾, ¾). These alloys obey the site preference rules where X and Y are d-group atoms, and Z is a p-group atom [25], which determines the site occupancy for X2YZ stoichiometry, as shown in Figure 1. De Paula et al. [26] and Burch et al. [27] proposed empirical site occupancy rules decades ago, indicating that the atoms of the p-group prefer (D) sites, whereas the (A, C) sites are occupied by the transition metals with more valence electrons, resulting in the highly ordered L21 structure. According to these rules, the (B) site was occupied by the other transition metal. Usually, the site preference of different 3d elements in Heusler alloys is determined by the number of their valence electrons [28]: elements with more valence electrons tend to enter the (A, C) sites and form a Cu2MnAl type of structure, while elements with fewer electrons prefer the B sites and form a Hg2CuTi type of structure; the main group elements usually occupy the D sites. We draw attention to the fact that these principles explain why individual atoms’ electronic valences are p or d [29]. Another possible order is that an inverse Heusler structure is created when the valence of the Y atom is larger than that of the X atom, with the Y atom occupying the (A) site and one of the X atoms being reallocated to the (B) site. A multitude of disordered alternate forms is associated with this L21 structure. The XA inverse Heusler structure is a cubic structure that belongs to the space group F43m and has CuHg2Ti as its prototype structure. It is a common occurrence in Mn2-based compounds.
For the purposes of this review, it is useful to present two types of distinct disordered structures. The B2-type disorder is created when the Y and Z atoms indistinctly occupy B and D sites. Thus, in the figure, green and red sites are equivalent, resulting in a symmetry-reduced cubic structure with the space group Pm3m.
Finally, a completely disordered structure named A2-type disordered structure can arise when all X, Y, and Z sites are equivalent, resulting in a body-centered cubic lattice with decreased symmetry and space group Im3m. Thus, in the crystallographic phase, a unique color can be used to draw all atoms. By way of summary, Table 1 shows the sites (A, B, C, and/or D) of the atoms of X, Y, and Z (for a stoichiometric composition).

2.3. Influence of p–d Hybridization

The creation of hybrid orbitals may be understood in light of traditional molecular orbital theory, which is responsible for defining the various forms of chemical bonding in solids [30]. The macroscopic mechanical behavior of materials is described by Ci,j elastic constants [31], which are directly dependent on the atomic chemical bonds. The correlation between the degree of p–d hybridization and mechanical properties of Ni2MnZ (Z = Al, Ga, In, Si, Ge, and Sn) has been recently investigated via first-principle calculations by Yan et al. [32]. This study illustrates how the choice of the p-group atom strongly affects the three elastic constants (C11, C12, and C44) characteristic of a cubic lattice. Typical X2MnZ Heusler specimens show a distinct structural phase transition, resulting in multi-functional characteristics. Winterlik et al. [33] reported the electronic structure calculations for Heusler alloys to investigate candidates for superconductivity and identified several Ni2-based Heusler alloys that become superconducting in the low-temperature region. The superconductivity aspect appears in the system (Eu1−xPrx)BCO [34]. As part of this MT, the material transitions from a high-temperature austenite phase with cubic symmetry to a low-temperature martensitic phase with decreasing symmetry. The fact that the atoms actively rearrange themselves using a shear-like process while keeping their relative positions is its most distinctive feature [35]. When it comes to controlling the MT temperature range, the level of the p–d orbital hybridization process between the p states of Z atoms and the d states of X atoms is also significant [36,37,38]. Moreover, the enhancement of mechanical properties of all-d-metal full Heusler alloys is the main achievement caused by the suppression of p–d hybridization, as depicted in Table 2. The lower values of Young’s elastic modulus exhibited by all-d-metal Heusler in comparison to conventional ones are related to its higher ductility since it is a quantitative parameter of the resistance to elastic deformation upon mechanical load [39,40,41,42,43].
From a practical standpoint, stoichiometric variation or partial atomic replacement can be used to tailor MT for specific applications. Both situations have a different number of electrons available for this interaction. The valence electron concentration per atom (e/a) measures this distinct property and is expressed as [39]:
(e/a) = ½[NXfX + NYfY+ NZfZ]/100,
where NX, NY, and NZ are the number of valence electrons of each element, and fX, fY, and fZ stand for their corresponding atomic percentages.
A linear dependency of MT versus the (e/a) ratio for many common X2MnZ Heusler compounds is usually found [22]. Likewise, the austenite (AS) to martensite (MS) structural transformation can be accompanied by the ferromagnetic (FM) to paramagnetic (PM) magnetic transformation. Depending on alloy and composition, this magnetic transformation can appear in the austenite or in the martensitic regions. Thus, all the combinations are possible: AS-FM, AS-PM, MS-FM, and MS-PM. Figure 2 shows a temperature transformation diagram. The slope of the martensitic start temperature (Ms) is influenced by choice of the p-element. Obviously, some of these alloys present another magnetic behavior as supermagnetism or spin glass [40].

2.4. MCE in Heusler Alloys

In 1983, Wachtel et al. [45] and Maeda et al. [46] produced the first studies on MCE of Heusler Ni2(Mn1−xMx)Sn with M = V and Nb(x = 0.1, 0.2, 0.3 and 0.4), Mn3-y-zCryAlC1+z (z = 0.1 and y = 0, 0.06, 0.15 and 0.26), and (y = 0 and z = −0.16, −0.08, 0 and 0.1) alloys. They discovered that Curie temperature (TC) values drop linearly from room temperature (RT) to around 200 K, and Msalsodecreases linearly. The biggest maximum values of magnetic entropy change (ΔSM) found in the system at x = 0.1 to 0.2 and in the latter one at y = 0 and z = 0.9 are roughly half of Gd, while (ΔSM)Max steadily declines with increasing x or y. Later, in 2000, at moderate fields (ΔSM = +4 Jkg−1K−1 at 0.9 T), Hu et al. [47] observed an inverse MCE attributed to MT (thermal hysteresis 10 K. Due to the substantial uniaxial magneto-crystalline anisotropy of the martensitic phase, inverse MCE arises when both phases are FM, and the high-temperature phase (austenite) has a stronger magnetization than the low-temperature phase (martensite) at low fields [48]. However, for fields larger than 1 T, inverse MCE is replaced with direct MCE [49,50]. A giant MCE [51] was discovered in the compositional area where the magnetostructural transition occurs. Zhou et al. [52,53] studied magnetic and structural transitions, as well as MCE, in Ni2MnGa alloys. Because Ni-rich alloys have a lower TC than Mn-rich alloys, their MT is closer to RT. By using neutron diffraction on Ni2MnGa and Ni1.75Mn1.25Ga systems, Singh et al. [54] recently showed that the inverse MCE is caused by the antiferromagnetic (AFM) contact between Mn atoms at in-equivalent sites. Figure 3 depicts the ΔSM values’ field dependency in two examples: adapted from reference Ni2MnGa and Ni2MnGa0.95Sn0.05 [55].
Sasso et al. [56], whose results are consistent with those of Khovaylo et al. [57], who attributed differences in field-applied and field-removed curves to magnetostructural hysteresis, also highlighted MCE’s historical dependence on the field and thermal sequence. Porcary et al. [58] established the convergence of direct and indirect methodologies in the analysis of Ni(Co)–Mn–Ga alloy. There are various arguments against using Heusler alloys as magnetic refrigerants, including the irreversible nature of the magnetic field-driven MT and the considerable hysteresis found [54]. As a result, researchers in MCE for Heusler alloys are presently focusing their efforts on removing hysteresis. Inverse giant MCE in Ni50Mn37Sn13 was reported by Krenke et al. [59] in 2005, while Han et al. [60] reported inverse giant MCE in In-containing Heusler alloys in 2006. Later, in 2007, Khan et al. [61] and Du et al. [62] indicated a good correlation for Ni2Mn1+xZ1−x (Z = In, Sn, and Sb) and Ni50-xMn37Sb13 alloys close to stoichiometric composition (x = 0.3) showing a cubic L21 austenitic phase and a typical FM/PM magnetic transition preserving this austenitic phase. However, alloys with a higher divergence from 2:1:1 stoichiometry show MT. In contrast to Ga-containing Heusler alloys, AFM coupling between Mn atoms is enhanced (martensitic state) in these alloys, resulting in a metamagnetic transformation from AFM to FM, which may be adjusted to be a meta-magneto-structural transition from AFM to FM austenitic phase. It has been proposed that the existence of both (direct and inverse) MCE is a mechanism for increased refrigeration cycle performance [63].
Due toits MCE, several Heusler alloy families have been studied. Temperatures surrounding the second-order phase transition (SOPT) of Ni–Mn–Ge have been observed [64], with TC decreasing as the Ni/Mn ratio increases. Ni–Fe–Ga [65], Ni–(Fe,Co)–Ga [66], and Co–Ni–Ga [67] are examples of Mn-free systems discovered in the literature. Due to its higher ductility, Ni–Fe–Ga has been advocated as a superior MCE material than Ni–Mn–Ga. Its MCE effect is field dependent, similar to Ni–Mn–Ga, and at low fields, it switches from inverse to conventional MCE. Co helps to align the Curie temperatures of martensite and austenite phases with the transition temperature of MT by shifting to higher levels. Moderate MCE values were reported: ΔSM (5 T) = 2.4 Jkg−1K−1 at 360 K [63]. On the other hand, the higher MCE values of Co50Ni22Ga28 alloy were reported: ΔSM (5 T) = 10.5 Jkg−1K−1 at 313.5 K, which was attributed to the MT between FM martensite and FM austenite [64]. On the other hand, its sharp ΔSM(T) curves are full width at half maximum (FWHM < 2 K), and the considerable thermal hysteresis of the MT (20 K) must be taken into account. Vivas et al. [68] studied the effects of the number of valence electrons on the MCE of half-metal Fe2MnSi(Ga) alloys and found a phenomenological linear relationship between ΔSM and this parameter. In summary, Figure 4 shows the ΔSM values at 5 T as a function of the transition temperatures of various Heusler alloys.

3. All-d-Metal Heusler Alloys

3.1. Background of These Kinds of Alloys

Recently, Wei et al. [22] suggested the notion of an all-d-metal Heusler based on d–d orbital hybridization. The authors of this seminal work established the term “all-d-metal” after discovering that the Heusler phase could be formed without the p-group atom. Experiments on the crystal structure of Zn2AuAg and Zn2CuAg compounds [69,70] may be traced all the way back to the 1960s. Both compounds have L21 organized and B2 disordered structures, according to these ancient publications. The Zn2AuAg, in particular, shows a B2 to L21 order-disorder transition, as evidenced by changes in structural order characteristics. On the other hand, their applications as FSMAs are limited due to the absence of FM ordering in these alloys, and no further research on these alloys has been conducted as far as we know. Both alloys now belong within the category of Heusler alloys since the notion of all-d-metal Heusler is widely known.

3.2. Crystalline Structure

In the recently found Ni2Mn2-yTiy and Ni2−yMn2Tiy systems, Ti atoms have the fewest valence electrons (3d24s2) compared to Ni (3d84s2) and Mn (3d54s2), and Wei et al. [22] predicted that Ti would occupy the D site. Both systems crystallize in a B2-type disordered structure, with the Mn excess atoms sharing the D site with Ti atoms in the Ni2Mn2-yTiy system, resulting in a strong AFM coupling due to the Mn(B)–Mn(D) interaction (Figure 5). The main difference with conventional Heusler alloys is the competence between the L21 and the inverse XA phases.
The Ni2−xCoxMn1.4Ti0.6 quaternary series was discovered by Wei et al. [19], who employed the strategy of introducing Co atoms at Ni sites to impose FM long-range ordering on the Ni–Mn–Ti system, resulting in the first FSMAs among all-d-metal Heusler alloys. Partially replacing Co atoms in Ni2MnZ systems has previously been investigated [71], resulting in a strong local Mn(B)–Co(A/C)–Mn(D) exchange coupling with FM ordering [72], overcoming the Mn(B)–Mn(D) AFM coupling inherent in the B2-type disordered lattice. Moreover, some experimental results observed that strong ferromagnetism provides direct evidence of this probable atomic configuration and of the ferromagnetic activation effect in the Ni(Co,Fe)–Mn–Ti all-d-metal Heusler alloys. For example, in Ni50−xCoxMn35Ti15 alloys, Co atoms that have been substituted for Ni atoms will also share the (A,C) sites with Ni atoms, leaving Mn and Ti with fewer valence electrons at the B/D sites. With the aid of the strong FM exchange interactions between nearest-neighbor Co-Mn atoms, the original AFM exchange coupling between Mn-Mn atoms in Ni-Mn-Ti alloys is converted into FM one, resulting in parallel alignment of the Mn-Co-Mn moments [19]. This phenomenon is known as the “ferromagnetic activation effect of the Co atom” [72]. FM ordering in Ni2−xFexMn1.4Ti0.6 alloys [73], in which Fe substitutes Co in the exchange coupling, is generated via a similar mechanism. Co (3d74s2) and Fe (3d64s2) atoms are considered to share the (A/C) sites with Ni (3d84s2) atoms in both series since their valence numbers are greater than those of Mn and Ti. Feng [74] used theoretical calculations on the X2MnTi (X = Pt and Pd) series to study the impact of Ti as a p-group atom replacement. The findings show that the L21 crystallographic structure is energetically stable for both compositions, with high valence Pd (4d85s2) and Pt (5d86s2) filling the (A/C) sites and Mn (3d54s2) occupy the (B) site, respectively. Ti prefers to remain in the D site. Han et al. [75] developed research for all-d-metal Heusler alloys X2−xMn1+xV (X = Pd, Ni, Pt, Ag, Au, Ir, Co; x = 1, 0). They looked at the atomic occupancy of these alloys in the cubic phase and discovered that the well-known site preference criterion does not apply to all of them. Han et al. [76,77] and Wang et al. [78] studied other Zinc-based all-d-metal Heusler ZnCdTMn combinations by theoretical calculations on the Zn2YMn series. As a result of its complete 3d occupied state, the Zn atoms behave as a major group element, and Zn atoms prefer to occupy the D site rather than replacing Pd atoms at site A. The phenomenon of this process is the whole 3d shell of the Zn atom.
In Figure 5, as the content of Ti was usually lower than 25 at.%, some Mn atoms are located on D sites by substituting Ti atoms. However, the martensitic crystallographic structure can be more complex, including modulation, as shown in Figure 6.

3.3. Influence of d–d Hybridization

Theoretical calculations revealed that stoichiometric Ni2MnTi displays mechanical properties superior to those of conventional Heusler systems. Yan et al. [79] later discovered that the Ni2.0Mn1.27Ti0.73 composition has a significant eCE (under 600 MPa of uniaxial stress, adiabatic temperature change ΔTad = −20.4 K). Many Ni–Mn-based systems, such as Ni1.80Mn1.76Sn0.44 (ΔTad = −11.6 K unloading 600 MPa of uniaxial stress) [80] and Ni2.0Mn1.11Ga0.89 (unloading 100 MPa of uniaxial stress, ΔTad = −6.1 K) [81], have lower values. Changing the chemical bonding character of the Ni2.0Mn1.27Ti0.73 all-d-metal Heusler alloy by substituting high p–d hybridization with somewhat weaker d–d hybridization among transition metals increases its ductility, according to further examination of the electron localization function. Pugh’s ratio [82] is a popular metric for determining solid ductility. It is defined as the ratio of the bulk modulus B to the shear modulus G of a material. Values greater than 1.75 indicate ductile behavior. For different X2MnZ compositions, Figure 7 illustrates Pugh’s ratio as a function of Cauchy pressure, a parameter that describes the dominant kind of chemical bonding. We see that Ni2MnTi is more ductile than Ni2MnGa [83] and Ni2MnIn [84], two of the most promising FSMAs among Heusler systems, according to our results. Furthermore, Ni2MnTi [85] also has the highest Cauchy pressure, indicating that chemical bandings are weakly covalent. As a consequence, reducing covalent p–d hybridization in Ni2MnZ Heusler alloys is connected to enhanced ductility.

3.4. MCE in All-d-Metal Heusler Alloys

Until recently, only a few investigations have focused on Heusler alloys of this type. Wei et al. [22] recently discussed the creation of all-d-metal alloys that exclusively include 3d transition metal components. They found that adding Ti to Ni–Mn aids in the B2 phase creation and stability. Cong et al. [6] achieved a massive elastocaloric impact in Ni–Mn–Ti alloys, with a ΔTad = 31.5 K and ΔSM = 45 Jkg−1K−1, at a pressure of 700 MPa. Yan et al. [77] also discovered that the bulk Ni50Mn31.75Ti18.25 alloy has outstanding mechanical characteristics, with a stress of 1.1 GPa and a convincing compressive strain of 13%, respectively. Despite its exceptional elastocaloric sway, the Ni–Mn–Ti combination has a modest MCE when compared to Heusler alloys. The absence of magnetic contrast between the austenite and martensite phases is largely responsible for this. Yan et al. [79] examined the austenite phase’s antiferromagnetic condition in Ni–Mn–Ti alloys. As a result, some thought has been given to doping the elements to improve the magnetocaloric impact. Furthermore, according to Wei et al. [19], cobalt doping in the Ni50Mn35Ti15 alloy affects the transition from AFM to FM in the austenite phase. They created the Mn–Co–Mn configuration by replacing Co for Ni sites in the austenite phase, resulting in the ferromagnetic activation effect. Additionally, the AFM state of austenite in Ni–Mn–Ti alloys was confirmed by Yan et al. [79] and Wei et al. [19]. Therefore, some researchers have attempted to improve its MCE by means of doping elements. Li et al. [86] indicated that under a magnetic field of 3 T, Fe and Co doping in the Ni–Mn–Ti alloy could produce the refrigeration capacity (RC) of 79.5 Jkg−1 and ΔSM of 8.4 Jkg−1K−1. In addition, taking into account the magnetostructural coupling in the Ni2−xFexMnTi [81] and Ni–Co–Mn–Ti [73] Heusler alloys, a giant MCE was observed. Recently, Aznar et al. [87,88] revealed the B-doped Ni50Mn31.5Ti18.5 all-d-metal Heusler alloy. These alloys created an excellent BCE with an RC up to 1100 Jkg−1 and ΔSM of 74 Jkg−1K−1 under the pressure of 3.8 kbar, undergoing MT with an enormous volume change (ΔV) in its PM. Due to the eCE and MCE coexisting near RT, these alloys must be candidates for magnetic refrigeration.

3.5. Perspectives

Recently, experimental efforts targeted at increasing the MCE of all-d-metal Heusler alloys are worth emphasizing. One option is to add more elements to analyze multicomponent specimens and the effect of the combination of four or fifth elements in the functional response in a similar pathway to the applied to conventional Heusler alloys. Taubel et al. [89] revealed that an ideal annealing technique sharpened the phase transformation in the quaternary Ni2−xCoxMn2−yTiy series, while the Co content governs the transition’s sensitivity to the external magnetic field. The direct MCE is particularly strong in the Ni1.40Co0.60Mn1.48Ti0.25 Heusler alloy (ΔT = 4.0 K and ΔSiso = −20.0 Jkg−1K−1 under an applied magnetic field of 20 kOe). Li and coworkers [90] made a significant addition to the field by investigating the Ni1.4Co0.6−xFexMn1.4Ti0.6 series experimentally. The partial replacement of Fe atoms with Co atoms decreases the d–d hybridizations, in this case, changing the Curie temperature and MT temperatures of the system. The maximum direct MCE value (ΔSiso = −20.0 Jkg−1K−1 under a field of 50 kOe) was found for the x = 0.024 composition. By applying hydrostatic pressure (0.35 GPa), the functional response is improved, achieving values of ΔSiso = −24.20 Jkg−1K−1 and RC = 347.26 JK−1 (under a field of 50kOe) [85]. Because this system has both direct and inverse MCE, both demagnetization and magnetization processes may be investigated for solid-state refrigeration.
It should be remarked that these materials are also under study for applications such as catalysis with chemically diverse surface configurations [91]. These materials can also have high magnetoresistance [92] and spintronic properties [93].
We advocate focusing future research on the atomic site occupancy rules of these kinds of alloys. First principles and density functional theory (DFT) studies will be useful in understanding atomic site influence on the total magnetic moment per formula unit [89,90,91,92,93,94]. It is known that a large reversible magnetocaloric effect and high magnetoresistance were achieved by improving the crystallographic compatibility between the austenitic and martensitic phases [95]. Likewise, the influence of d–d hybridizations on atomic ordering may be shown by evaluating structural and magnetic properties when the quantity of the p-atom group decreases. Furthermore, the impact of thermal annealing, applied pressure as well as several synthesis methods on the creation of the L21 phase should be further investigated. Finally, because of the increased mechanical ductility and high induced strain values observed, the shape memory impact of ternary Ni2xMn1+xTixand Mn2xNi1+xTix series should be further investigated.

4. Conclusions

By removing the p-group atom from the X2YZ composition, novel functional all-d-metal Heusler alloys are developed. These findings contribute to our knowledge of the role of orbital hybridization in the fundamental and functional features of X2YZ Heusler alloys. According to the current study, despite the lack of a p-group atom, the martensitic transition with adjustable MT by chemical composition occurs. Finally, substituting a transition metal for the p-group enhances mechanical ductility and results in considerable reversible MCE. The suppression of p–d hybridization and the growth of d–d hybridizations is the key physical process that combines remarkable mechanical features with huge MCE. Because of their optimal functional behavior, these alloys are a possible new class of materials for technological applications. We advocate focusing future research on the atomic site occupancy rules of these kinds of alloys. The influence of d–d hybridizations on atomic ordering may be shown by evaluating structural and magnetic properties when the quantity of the p-atom group decreases. Furthermore, the impact of thermal annealing techniques, as well as several synthesis methods on the creation of the L21 phase, should be further investigated. Finally, because of the increased mechanical ductility and high induced strain values observed, the shape memory impact of ternary Ni2xMn1+xTixand Mn2xNi1+xTix series should be further investigated.

Author Contributions

Conceptualization, T.B.; methodology, T.B. and J.-J.S.; writing—original draft preparation, T.B.; writing—review and editing, J.-J.S. and T.B. All authors have read and agreed to the published version of the manuscript.

Funding

This study was funded by the University of Girona PONT2020-01 and Mineco Spain MAT2016-75967-P projects.

Data Availability Statement

Data can be requested from the authors.

Acknowledgments

The authors acknowledge A. Carrillo for the MAUD crystallography images support.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Laurence Livermore National Laboratory. Energy Flow Charts. Available online: https://flowcharts.llnl.gov/commodities/energy (accessed on 22 November 2022).
  2. Gutfleisch, O.; Willard, M.A.; Bruck, E.; Chen, C.H.; Sankar, S.G.; Liu, J.P. Magnetic Materials and Devices for the 21st Century: Stronger, Lighter, and More Energy Efficient. Adv. Mater. 2011, 23, 821–842. [Google Scholar] [CrossRef] [PubMed]
  3. Wu, Y.F.; Xuan, H.C.; Agarwal, S.; Xu, Y.K.; Zhang, T.; Feng, L.; Li, H.; Han, P.D.; Zhang, C.L.; Wang, D.H.; et al. Large magnetocaloric effect and magnetoresistance in Fe and Co co-doped Ni-Mn-Al Heusler alloys. Phys. Status Solidi A 2018, 215, 1700843. [Google Scholar] [CrossRef]
  4. Franco, V.; Blázquez, J.S.; Ipus, J.J.; Law, J.Y.; Moreno-Ramírez, L.M.; Conde, A. Magnetocaloric effect: From materials research to refrigeration devices. Prog. Mater. Sci. 2018, 93, 112–232. [Google Scholar]
  5. Stern-Taulats, E.; Planes, A.; Lloveras, P.; Barrio, M.; Tamarit, J.L.; Pramanick, S.; Majumdar, S.; Yüce, S.; Emre, B.; Frontera, C.; et al. Tailoring barocaloric and magnetocaloric properties in low-hysteresis magnetic shape memory alloys. Acta Mater. 2015, 96, 324–332. [Google Scholar] [CrossRef] [Green Version]
  6. Cong, D.Y.; Xiong, W.X.; Planes, A.; Ren, Y.; Mañosa, L.; Cao, P.Y.; Nie, Z.H.; Sun, X.M.; Yang, Z.; Hong, X.F.; et al. Colossal elastocaloric effect in ferroelastic Ni-Mn-Ti alloys. Phys. Rev. Lett. 2019, 122, 255703. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  7. Bonnot, E.; Romero, R.; Mañosa, L.; Vives, E.; Planes, A. Elastocaloric effect associated with the martensitic transition in shape-memory alloys. Phys. Rev. Lett. 2008, 100, 125901. [Google Scholar] [CrossRef] [Green Version]
  8. Bachaga, T.; Zhang, J.; Khitouni, M.; Sunol, J.J. NiMn-based Heusler magnetic shape memory alloys: A review. Int. J. Adv. Manuf. Technol. 2019, 103, 2761–2772. [Google Scholar] [CrossRef]
  9. Soto-Parra, D.E.; Vives, E.; González-Alonso, D.; Manosa, L.; Planes, A.; Romero, R.J.; Matutes-Aquino, A.; Ochoa-Gamboa, R.A.; Flores-Zúniga, H. Stress and magnetic field-induced entropy changes in Fe-doped Ni–Mn–Ga shape-memory alloys. Appl. Phys. Lett. 2010, 96, 071912. [Google Scholar] [CrossRef]
  10. Castillo-Villa, P.O.; Soto-Parra, D.E.; Matutes-Aquino, J.A.; Ochoa-Gamboa, R.A.; Planes, A.; Manosa, L.; González-Alonso, D.; Stipcich, M.; Romero, R.; Ríos-Jara, D.; et al. Caloric effects induced by magnetic and mechanical fields in a Ni50Mn25−xGa25Cox magnetic shape memory alloy. Phys. Rev. B 2011, 83, 174109. [Google Scholar] [CrossRef]
  11. Khan, M.T.; Wang, Y.; Wang, C.; Liao, X.; Yang, S.; Song, X.; Ren, X. Combination of conventional elastocaloric and magnetocaloric effects in a Co37Ni35Al28 ferromagnetic shape memory alloy. Scr. Mater. 2018, 146, 182. [Google Scholar] [CrossRef]
  12. Castillo-Villa, P.O.; Manosa, L.; Planes, A.; Soto-Parra, D.E.; Sánchez-Llamazares, J.L.; Flores-Zúniga, H.; Frontera, C. Elastocaloric and magnetocaloriceffects in Ni-Mn-Sn(Cu) shapememoryalloy. J. Appl. Phys. 2013, 113, 053506. [Google Scholar] [CrossRef]
  13. Qu, Y.H.; Cong, D.Y.; Li, S.H.; Gui, W.Y.; Nie, Z.H.; Zhang, M.H.; Ren, Y.; Wang, Y.D. Simultaneously achieved large reversible elastocaloric and magnetocaloric effects and their coupling in a magnetic shape memory alloy. Acta Mater. 2018, 151, 41. [Google Scholar] [CrossRef]
  14. Huang, C.; Wang, Y.; Tang, Z.; Liao, X.; Yang, S.; Song, X. Influence of atomic ordering on elastocaloric and magnetocaloric effects of a Ni–Cu–Mn–Ga ferromagnetic shape memory alloy. J. Alloys Compd. 2015, 630, 244. [Google Scholar] [CrossRef]
  15. Li, Y.; Sun, W.; Zhao, D.; Xu, H.; Liu, J. An 8 K elastocaloric temperature change induced by 1.3% transformation strain in Ni44Mn45−xSn11Cux alloys. Scr. Mater. 2017, 130, 278. [Google Scholar] [CrossRef]
  16. Tang, X.; Feng, Y.; Wang, H.; Wang, P. Enhanced elastocaloric effect and cycle stability in B and Cu co-doping Ni-Mn-In polycrystals. Appl. Phys. Lett. 2019, 114, 033901. [Google Scholar] [CrossRef]
  17. Yang, Z.; Cong, D.Y.; Sun, X.M.; Nie, Z.H.; Wang, Y.D. Enhanced cyclability of elastocaloric effect in boron-microalloyed Ni-Mn-In magnetic shape memory alloys. Acta Mater. 2017, 127, 33. [Google Scholar] [CrossRef]
  18. Li, Z.B.; Yang, J.J.; Li, D.; Li, Z.Z.; Yang, B.; Yan, H.L.; Sánchez-Valdés, C.F.; Sánchez Llamazares, J.L.; Zhang, Y.D.; Esling, C.; et al. Tuning the reversible magnetocaloric effect in Ni–Mn–In-based alloys through Co and Cu Co-doping. Adv. Electron. Mater. 2019, 5, 1800845. [Google Scholar] [CrossRef]
  19. Wei, Z.Y.; Liu, E.K.; Chen, J.H.; Li, Y.; Liu, G.D.; Luo, H.Z.; Xi, X.K.; Zhang, H.W.; Wang, W.H.; Wu, G.H. Realization of multifunctional shape memory ferromagnets in all-d-metal Heusler phases. Appl. Phys. Lett. 2015, 107, 022406. [Google Scholar] [CrossRef] [Green Version]
  20. Tusek, J.; Žerovnik, A.; Čebron, M.; Brojan, M.; Žužek, B.; Engelbrecht, K.; Cadelli, A. Elastocaloric effect vs fatigue life: Exploring the durability limits of Ni-Ti plates under pre-strain conditions for elastocaloric cooling. Acta Mater. 2018, 150, 295–307. [Google Scholar] [CrossRef] [Green Version]
  21. Liu, J.; Zhao, D.; Li, Y. Exploring magnetic elastocaloric materials for solid-state cooling. Shap. Mem. Superelasticity 2017, 3, 192–198. [Google Scholar] [CrossRef]
  22. Wei, Z.Y.; Liu, E.K.; Li, Y.; Han, X.L.; Du, Z.W.; Luo, H.Z.; Liu, G.D.; Xi, X.K.; Zhang, H.W.; Wang, W.H.; et al. Magnetostructural martensitic transformations with large volume changes and magnetostrains in all-d-metal Heusler alloys. Appl. Phys. Lett. 2016, 109, 071904. [Google Scholar] [CrossRef]
  23. Meinert, M.; Schmalhorst, J.M.; Reiss, G.; Arenholz, E. Ferrimagnetism and disorder of epitaxial Mn2−xCoxVAl Heusler compound thin films. J. Phys. D Appl. Phys. 2011, 44, 215003. [Google Scholar] [CrossRef] [Green Version]
  24. Graf, T.; Felser, C.; Parkin, S.S.P. Simple rules for the understanding of Heusler compounds. Prog. Solid State Chem. 2011, 39, 1–50. [Google Scholar] [CrossRef]
  25. Li, G.J.; Liu, E.K.; Zhang, H.G.; Qian, J.F.; Zhang, H.W.; Chen, J.L.; Wang, W.H.; Wu, G.H. Unusual lattice constant changes and tunable magnetic moment compensation in Mn50−xCo25Ga25+x alloys. Appl. Phys. Lett. 2012, 101, 102402. [Google Scholar] [CrossRef]
  26. De Paula, V.G.; Reis, M.S. All-d-metal full Heusler alloys: A novel class of functional materials. Chem. Mater. 2021, 33, 5483–5495. [Google Scholar] [CrossRef]
  27. Niculescu, V.; Burch, T.J.; Raj, K.; Budnick, J.I. Properties of Heusler-type materials Fe2TSi and FeCo2Si. J. Magn. Magn. Mater. 1977, 5, 60–66. [Google Scholar] [CrossRef]
  28. Kandpal, H.C.; Fecher, G.H.; Felser, C. Calculated electronic and magnetic properties of the half-metallic, transition metal based Heusler compounds. J. Phys. D Appl. Phys. 2007, 40, 1507. [Google Scholar] [CrossRef] [Green Version]
  29. Ma, L.; Wang, W.H.; Zhen, C.M.; Hou, D.L.; Tang, X.D.; Liu, E.K.; Wu, G.H. Polymorphic magnetization and local ferromagnetic structure in Co-doped Mn2NiGa alloys. Phys. Rev. B Condens. Matter Mater. Phys. 2011, 84, 224404. [Google Scholar] [CrossRef] [Green Version]
  30. Pauling, L. The nature of the chemical bond. Application of results obtained from the quantum mechanics and from a theory of paramagnetic susceptibility to the structure of molecules. J. Am. Chem. Soc. 1931, 53, 1367–1400. [Google Scholar] [CrossRef]
  31. Kittel, C.; McEuen, P. Introduction to Solid State Physics; Wiley: New York, NY, USA, 1976; p. 8. [Google Scholar]
  32. Yan, H.L.; Liu, H.X.; Zhang, M.J.; Jia, N.; Bai, J.; Yang, B.; Li, Z.; Zhang, Y.; Esling, C.; Zhao, X.; et al. Electronic origin of the main-group element dependences of elastic moduli in the Ni2Mn-based magnetic shape memory alloys. J. Phys. Chem. Solids 2021, 148, 109671. [Google Scholar] [CrossRef]
  33. Winterlik, J.; Fecher, G.H.; Felser, C.; Jourdan, M.; Grube, K.; Hardy, F.; Löhneysen, H.V.; Holman, K.L.; Cava, R.J. Ni-based superconductor: Heusler compound ZrNi2Ga. Phys. Rev. B 2008, 78, 184506. [Google Scholar] [CrossRef]
  34. Peczkowski, P.; Zachariasz, P.; Jastrzebski, C.; Pietosa, J.; Drzymała, E.; Gondek, Ł. On the Superconductivity Suppression in Eu1−xPrxBa2Cu3O7−δ. Materials 2021, 14, 3503. [Google Scholar] [CrossRef] [PubMed]
  35. Khachaturyan, A.G. Theory of Structural Trans-Formations in Solids; Courier Corporation: New York, NY, USA, 2013. [Google Scholar]
  36. Roy, S.; Blackburn, E.; Valvidares, S.M.; Fitzsimmons, M.R.; Vogel, S.C.; Khan, M.; Dubenko, I.; Stadler, S.; Ali, N.; Sinha, S.K.; et al. Delocalization and hybridization enhance the magnetocaloric effect in Cu-doped Ni2MnGa. Phys. Rev. B Condens. Matter Mater. Phys. 2009, 79, 235127. [Google Scholar] [CrossRef]
  37. Li, G.J.; Liu, E.K.; Zhang, H.G.; Zhang, Y.J.; Xu, G.Z.; Luo, H.Z.; Zhang, H.W.; Wang, W.H.; Wu, G.H. Role of covalent hybridization in the martensitic structure and magnetic properties of shape-memory alloys: The case of Ni50Mn5+xGa35−xCu10. Appl. Phys. Lett. 2013, 102, 062407. [Google Scholar] [CrossRef] [Green Version]
  38. Krenke, T.; Moya, X.; Aksoy, S.; Acet, M.; Entel, P.; Mañosa, L.; Planes, A.; Elerman, Y.; Yücel, A.; Wassermann, E.F. Electronic aspects of the martensitic transition in Ni−Mn based Heusler alloys. J. Magn. Magn. Mater. 2007, 310, 2788–2789. [Google Scholar] [CrossRef]
  39. Yang, S.; Kong, Y.; Du, Y.; Shen, L.; Shen, Y. First-principles prediction of structural, mechanical and magnetic properties in Ni2MnAl. Comput. Mater Sci. 2016, 123, 52–58. [Google Scholar] [CrossRef]
  40. Liu, K.; Ma, S.; Ma, C.; Han, X.; Yu, K.; Yang, S.; Zhang, Z.; Song, Y.; Luo, X.; Chen, C.; et al. Martensitic transformation and giant magnetofunctional properties in all-d-metal Ni-Co-Mn-Ti alloy ribbons. J. Alloys Compd. 2019, 790, 78–92. [Google Scholar] [CrossRef]
  41. Roy, T.; Gruner, M.E.; Entel, P.; Chakrabarti, A. Effect of substitution on elastic stability, electronic structure and magnetic property of Ni−Mn based Heusler alloys: An ab initio comparison. J. Alloys Compd. 2015, 632, 822–829. [Google Scholar] [CrossRef]
  42. Ahamed Khan, R.; Ghomashchi, R.; Xie, Z.; Chen, L. Ferromagnetic shape memory Heusler materials: Synthesis, microstructure characterization and magneto-structural properties. Materials 2018, 11, 988. [Google Scholar] [CrossRef] [Green Version]
  43. Suh, B.; Baek, S.J.; Rhee, J.Y. Antisite disorder and super-paramagnetism in Heusler-like Fe2Val: A 51V and 27Al NMR study. J. Korean Phys. Soc. 2006, 4, 288–291. [Google Scholar]
  44. Ameur, R.; Chemingui, M.; Bahaga, T.; Escoda, L.; Khitouni, M.; Suñol, J.J. Martensitic transformation and crystalline structure of Ni50Mn50−xSnx melt-spun Heusler alloys. Crystals 2020, 10, 853. [Google Scholar] [CrossRef]
  45. Wachtel, E.; Henninger, F.; Predel, B. Constitution and magnetic-properties of Ni-Mn-Sn alloys-solid and liquid-state. J. Magn. Magn. Mater. 1983, 38, 305–315. [Google Scholar] [CrossRef]
  46. Maeda, H.; Sato, M.; Uehara, M. Dawn of research on magnetic refrigeration materials at the National Institute for Materials Research, Science and Technology Agency. J. Jpn. Inst. Metals 1983, 47, 683–687. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  47. Hu, F.X.; Shen, B.G.; Sun, J.R. Magnetic entropy change in Ni51.5Mn22.7Ga25.8 alloy. Appl. Phys. Lett. 2000, 76, 3460–3462. [Google Scholar] [CrossRef]
  48. Fukuda, T.; Maeda, H.; Yasui, M.; Kakeshita, T. Influence of magnetocrystalline anisotropy on martensitic transformation under magnetic field of single-crystalline Ni2MnGa. Scr. Mater. 2009, 60, 261–263. [Google Scholar] [CrossRef]
  49. Hu, F.X.; Sun, J.R.; Wu, G.H.; Shen, B.G. Magnetic entropy change involving martensitic transition in NiMn-based Heusler alloys. J. Appl. Phys. 2001, 90, 5216–5219. [Google Scholar] [CrossRef]
  50. Hu, F.X.; Shen, B.G.; Sun, J.R.; Wu, G.H. Large magnetic entropy change in a Heusler alloy Ni52.6Mn23.1Ga24.3 single cristal. Phys. Rev. B. 2001, 64, 132412. [Google Scholar] [CrossRef] [Green Version]
  51. Mandal, K.; Pal, D.; Scheerbaum, N.; Lyubina, J.; Gutfleisch, O. Magnetocaloric effect in Ni–Mn–Ga alloys. IEEE Trans. Magn. 2008, 44, 2993–2996. [Google Scholar] [CrossRef]
  52. Zhou, X.Z.; Li, W.; Kunkel, H.P.; Williams, G. Influence of the nature of the magnetic phase transition on the associated magnetocaloric effect in the Ni–Mn–Ga system. J. Magn. Magn. Mater. 2005, 293, 854–862. [Google Scholar] [CrossRef]
  53. Zhou, X.Z.; Kunkel, H.; Williams, G.; Zhang, S.H.; Xue, D.H. Phase transitions and the magnetocaloric effect in Mn rich Ni–Mn–Ga Heusler alloys. J. Magn. Magn. Mater. 2006, 305, 372–376. [Google Scholar] [CrossRef]
  54. Singh, S.; Esakki Muthu, S.; Senyshyn, A.; Rajput, P.; Suard, E.; Arumugam, S.; Barman, S.R. Inverse magnetocaloric effect in Mn2NiGa and Mn1.75Ni1.25Ga magnetic shape memory alloys. Appl. Phys. Lett. 2014, 104, 051905. [Google Scholar] [CrossRef]
  55. Chatterjee, S.; Giri, S.; Majumdar, S.; De, S.K.; Koledov, V.V. Magnetic properties of full Heusler alloys Ni2MnGa1−xZx with Z = Sn or Zn. J. Magn. Magn. Mater. 2012, 324, 1891–1896. [Google Scholar] [CrossRef]
  56. Sasso, C.P.; Kuepferling, M.; Giudici, L.; Basso, V.; Pasquale, M. Direct measurements of the entropy change and its history dependence in Ni–Mn–Ga alloys. J. Appl. Phys. 2008, 103, 07B306. [Google Scholar] [CrossRef]
  57. Khovaylo, V. Inconvenient magnetocaloric effect in ferromagnetic shape memory alloys. J. Alloys Compd. 2013, 577, S362–S366. [Google Scholar] [CrossRef]
  58. Porcari, G.; Cugini, F.; Fabbrici, S.; Pernechele, C.; Albertini, F.; Buzzi, M.; Mangia, M.; Solzi, M. Convergence of direct and indirect methods in the magnetocaloric study of first order transformations: The case of Ni–Co–Mn–Ga Heusler alloys. Phys. Rev. B 2012, 86, 104432. [Google Scholar] [CrossRef]
  59. Krenke, T.; Duman, E.; Acet, M.; Wassermann, E.F.; Moya, X.; Mañosa, L.; Planes, A. Inverse magnetocaloric effect in ferromagnetic Ni–Mn–Sn alloys. Nat. Mater. 2005, 4, 450–454. [Google Scholar] [CrossRef] [Green Version]
  60. Han, Z.D.; Wang, D.H.; Zhang, C.L.; Tang, S.L.; Gu, B.X.; Du, Y.W. Large magnetic entropy changes in the Ni45.4Mn41.5In13.1 ferromagnetic shape memory alloy. Appl. Phys. Lett. 2006, 89, 182507. [Google Scholar] [CrossRef]
  61. Khan, M.; Ali, N.; Stadler, S. Inverse magnetocaloric effect in ferromagnetic Ni50Mn37+𝑥Sb13−𝑥Heusler alloys. J. Appl. Phys. 2007, 101, 053919. [Google Scholar] [CrossRef] [Green Version]
  62. Du, J.; Zheng, Q.; Ren, W.J.; Feng, W.J.; Liu, X.G.; Zhang, Z.D. Magnetocaloric effect and magnetic-field-induced shape recovery effect at room temperature in ferromagnetic Heusler alloy Ni–Mn–Sb. J. Phys. D Appl. Phys. 2007, 40, 5523–5526. [Google Scholar] [CrossRef]
  63. Titov, I.; Acet, M.; Farle, M.; González-Alonso, D.; Mañosa, L.; Planes, A.; Krenke, T. Hysteresis effects in the inverse magnetocaloric effect in martensitic Ni–Mn–In and Ni–Mn–Sn. J. Appl. Phys. 2012, 112, 073914. [Google Scholar] [CrossRef]
  64. Si, P.Z.; Liu, J.J.; Chen, C.Q.; Wu, Q.; Jiao, Z.W.; Ge, H.L. The effect of Ni-substitution on the magnetic properties of Ni2MnGe Heusler alloys. J. Alloys Compd. 2008, 462, 1–3. [Google Scholar] [CrossRef]
  65. Yu, H.J.; Fu, H.; Zeng, Z.M.; Sun, J.X.; Wang, Z.G.; Zhou, W.L.; Zua, X.T. Phase transformations and magnetocaloric effect in NiFeGa ferromagnetic shape memory alloy. J. Alloys Compd. 2009, 477, 732–735. [Google Scholar] [CrossRef]
  66. Liu, J.; Scheerbaum, N.; Hinz, D.; Gutfleisch, O. A high-temperature coupling of martensitic and magnetic transformations and magnetic entropy change in Ni–Fe–Ga–Co alloys. Scr. Mater. 2008, 59, 1063–1066. [Google Scholar] [CrossRef]
  67. Fu, H.; Yu, H.J.; Teng, B.H.; Zhang, X.Y.; Zu, X.T. Magnetic properties and magnetic entropy change of Co50Ni22Ga28 alloy. J. Alloys Compd. 2009, 474, 595–597. [Google Scholar] [CrossRef]
  68. Vivas, R.J.C.; Pedro, S.S.; Cruz, C.; Tedesco, J.C.G.; Coelho, A.A.; Carvalho, A.M.G.; Rocco, D.L.; Reis, M.S. Experimental evidences of enhanced magnetocaloric properties at room temperature and half-metallicity on Fe2MnSi-based Heusler alloys. Mater. Chem. Phys. 2016, 174, 23–27. [Google Scholar] [CrossRef]
  69. Murakami, Y.; Watanabe, Y.; Kachi, S. An X-ray Study of the Heusler-type Ordering in AuAgZn2 Alloy. Trans. Jpn. Inst. Met. 1980, 21, 708–713. [Google Scholar] [CrossRef] [Green Version]
  70. Muldawer, L. X-ray study of ternary ordering of the noble metals in AgAuZn2 and CuAuZn2. J. Appl. Phys. 1966, 37, 2062–2066. [Google Scholar] [CrossRef]
  71. Ma, L.; Zhang, H.W.; Yu, S.Y.; Zhu, Z.Y.; Chen, J.L.; Wu, G.H.; Liu, H.Y.; Qu, J.P.; Li, Y.X. Magnetic-field-induced martensitic transformation in MnNiGa:Co alloys. Appl. Phys. Lett. 2008, 92, 032509. [Google Scholar] [CrossRef]
  72. Kainuma, R.; Imano, Y.; Ito, W.; Morito, H.; Sutou, Y.; Oikawa, K.; Fujita, A.; Ishida, K.; Okamoto, S.; Kitakami, O.; et al. Metamagnetic shape memory effect in a Heusler-type Ni43Co7Mn39Sn11 polycrystalline alloy. Appl. Phys. Lett. 2006, 88, 192513. [Google Scholar] [CrossRef]
  73. Zeng, Q.; Shen, J.; Zhang, H.; Chen, J.; Ding, B.; Xi, X.; Liu, E.; Wang, W.; Wu, G. Electronic behaviors during martensitic transformations in all-d-metal Heusler alloys. J. Phys. Condens. Matter. 2019, 31, 425401. [Google Scholar] [CrossRef]
  74. Feng, L. Investigation on martensitic transformation and magnetic properties of all-d-metal Pd2MnTi and Pt2MnTi by first-principle calculations. J. Supercond. Novel Magn. 2020, 33, 2245–2250. [Google Scholar] [CrossRef]
  75. Han, Y.; Wu, M.; Feng, Y.; Cheng, Z.; Lin, T.; Yang, T.; Wang, X. Competition between cubic and tetragonal phases in all-d-metal Heusler alloys, X2−xMn1+xV (X = Pd, Ni, Pt, Ag, Au, Ir, Co; x = 1, 0): A new potential direction of the Heusler family. IUCrJ 2019, 6, 465–472. [Google Scholar] [CrossRef] [PubMed]
  76. Han, Y.; Wu, M.; Kuang, M.; Yang, T.; Chen, X.; Wang, X. All-d-metal equiatomic quaternary Heusler hypothetical alloys ZnCdTMn (T =Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt): A first-principle investigation of electronic structures, magnetism, and possible martensitic transformations. Results Phys. 2018, 11, 1134–1141. [Google Scholar] [CrossRef]
  77. Han, Y.; Bouhemadou, A.; Khenata, R.; Cheng, Z.; Yang, T.; Wang, X. Prediction of possible martensitic transformations in all-d-metal Zinc-based Heusler alloys from first-principles. J. Magn. Magn. Mater. 2019, 471, 49–55. [Google Scholar] [CrossRef]
  78. Wang, X.; Wu, M.; Yang, T.; Khenata, R. Effect of Zn doping on phase transition and electronic structures of Heusler-type Pd2Cr-based alloys: From normal to all-d-metal Heusler. RSC Adv. 2020, 10, 17829–17835. [Google Scholar] [CrossRef]
  79. Yan, H.L.; Wang, L.D.; Liu, H.X.; Huang, X.M.; Jia, N.; Li, Z.B.; Yang, B.; Zhang, Y.D.; Esling, C.; Zhao, X.; et al. Giant elastocaloric effect and exceptional mechanical properties in an all-d-metal Ni-Mn-Ti alloy: Experimental and ab-initio studies. Mater. Des. 2019, 184, 108180. [Google Scholar] [CrossRef]
  80. Shen, Y.; Sun, W.; Wei, Z.Y.; Shen, Q.; Zhang, Y.F.; Liu, J. Orientation dependent elastocaloric effect in directionally solidified Ni-Mn-Sn alloys. Scr. Mater. 2019, 163, 14–18. [Google Scholar] [CrossRef]
  81. Wei, L.; Zhang, X.; Liu, J.; Geng, L. Orientation dependent cyclic stability of the elastocaloric effect in textured Ni-Mn-Ga alloys. AIP Adv. 2018, 8, 055312. [Google Scholar] [CrossRef] [Green Version]
  82. Everhart, W.; Newkirk, J. Mechanical properties of Heusler alloys. Heliyon 2019, 5, e01578. [Google Scholar] [CrossRef] [Green Version]
  83. Ozdemir Kart, S.; Cagin, T. Elastic properties of Ni2MnGa from first-principles calculations. J. Alloys Compd. 2010, 508, 177–183. [Google Scholar] [CrossRef]
  84. Agduk, S.; Gökoğlu, G. First-principles study of elastic and vibrational properties of Ni2MnIn magnetic shape memory alloys. Eur. Phys. J. B 2011, 79, 509–514. [Google Scholar] [CrossRef]
  85. Li, Y.; Huang, S.; Wang, W.; Liu, E.; Li, L. Ferromagnetic martensitic transformation and large magnetocaloric effect in Ni35Co15−xFexMn35Ti15 (x = 2, 4, 6, 8) alloys. J. Appl. Phys. 2020, 127, 233907. [Google Scholar] [CrossRef]
  86. Li, Y.; Qin, L.; Huang, S.; Li, L. Enhanced magnetocaloric performances and tunable martensitic transformation in Ni35Co15Mn35−xFexTi15 all-d-metal Heusler alloys by chemical and physical pressures. Sci. China Mater. 2022, 65, 486. [Google Scholar] [CrossRef]
  87. Aznar, A.; Gràcia-Condal, A.; Planes, A.; Lloveras, P.; Barrio, M.; Tamarit, J.; Xiong, W.; Cong, D.; Popescu, C.; Mañosa, L. Giant barocaloric effect in all-d-metal Heusler shape memory alloys. Phys. Rev. Mater. 2019, 3, 044406. [Google Scholar] [CrossRef] [Green Version]
  88. Aznar, A.; Gràcia-Condal, A.; Planes, A.; Lloveras, P.; Barrio, M.; Tamarit, J.L.; Xiong, W.; Cong, D.; Popescu, C.; Mañosa, L. DFT investigation on the electronic, magnetic, mechanical properties and strain effects of the quaternary compound Cu2FeSnS4. Crystals 2020, 10, 509. [Google Scholar]
  89. Taubel, A. Tailoring magnetocaloric effect in all-d-metal Ni-Co-Mn-Ti Heusler alloys: A combined experimental and theoretical study. Acta Mater. 2020, 201, 425. [Google Scholar] [CrossRef]
  90. Li, G.; Liu, E.; Wu, G. d-d hybridization controlled large-volume-change martensitic phase transition in Ni-Mn-Ti based all-d-metal Heusler compounds. J. Alloys Compd. 2022, 923, 166369. [Google Scholar] [CrossRef]
  91. Samanta, S.; Ghosh, S.; Chatterjee, M.K. Large magnetocaloric effect and magnetoresistance in Fe-Co doped Ni50-x(FeCo)xMn37Sn13 all-d-metal Heusler alloys. J. Alloys Compd. 2022, 910, 164929. [Google Scholar] [CrossRef]
  92. Wu, M.; Zhou, F.; Khenato, R.; Kuang, M.; Wang, X. Phase transition and electronic studies of all-d-metal Heusler-type X2nTi compounds (X = Pd, Pt, Ag, Au, Cu and Ni). Front. Chem. 2020, 8, 546947. [Google Scholar] [CrossRef]
  93. Zhang, F.; Westra, K.; Shen, Q.; Batashev, I.; Kiecana, A.; van Dijk, N. The second-order magnetic phase transition and magnetocaloric effect in all-d-metal NiCoMnTi based Heusler alloy. J. Alloys Compd. 2022, 906, 164337. [Google Scholar] [CrossRef]
  94. Jin, T.; Jung, Y. Classifying intermetallic tetragonal phase of all-d-metal Heusler alloys for catalysis applications. Top. Catal. 2022, 65, 208–214. [Google Scholar] [CrossRef]
  95. Samanta, S.; Chatterjee, S.; Ghosh, S.; Mandal, K. Large reversible magnetocaloric effect and magnetoresistance by improving crystallographic compatibility condition in Ni(Co)-Mn-Ti all-d-metal Heusler alloys. Phys. Rev. Mater. 2022, 6, 094411. [Google Scholar] [CrossRef]
Metals 13 00111 g001 550
Figure 1. Crystallographic structure of X2YZ Heusler alloys is shown in this diagram. Blue (A sites), green (B sites), yellow (C sites), and red (D sites).
Figure 1. Crystallographic structure of X2YZ Heusler alloys is shown in this diagram. Blue (A sites), green (B sites), yellow (C sites), and red (D sites).
Metals 13 00111 g001
Metals 13 00111 g002 550
Figure 2. Temperature (martensitic start Ms) transformation diagram topic of Heusler alloys (Reprinted with permission from ref. [44]. Copyright 2022 MDPI).
Figure 2. Temperature (martensitic start Ms) transformation diagram topic of Heusler alloys (Reprinted with permission from ref. [44]. Copyright 2022 MDPI).
Metals 13 00111 g002
Metals 13 00111 g003 550
Figure 3. Field dependence of ΔSM for Ni2MnGa1−xSnx (x = 0 and 0.05) alloys. Reproduced from reference [55]. Copyright 2012 Elsevier.
Figure 3. Field dependence of ΔSM for Ni2MnGa1−xSnx (x = 0 and 0.05) alloys. Reproduced from reference [55]. Copyright 2012 Elsevier.
Metals 13 00111 g003
Metals 13 00111 g004 550
Figure 4. ΔSM values for several Heusler alloys as a function of peak temperatures (Tpeak) at 5 T. Reprinted with the permission from refs. [65,66,67,68]. Copyrights 2008, 2009 and 2016 Elsevier.
Figure 4. ΔSM values for several Heusler alloys as a function of peak temperatures (Tpeak) at 5 T. Reprinted with the permission from refs. [65,66,67,68]. Copyrights 2008, 2009 and 2016 Elsevier.
Metals 13 00111 g004
Metals 13 00111 g005 550
Figure 5. Schema of the L21 Heusler crystallographic structure (left) indicating with red lines the cell of the L10 tetragonal martensite (right) for stoichiometric Ni50Mn25Ti25 alloy.
Figure 5. Schema of the L21 Heusler crystallographic structure (left) indicating with red lines the cell of the L10 tetragonal martensite (right) for stoichiometric Ni50Mn25Ti25 alloy.
Metals 13 00111 g005
Metals 13 00111 g006 550
Figure 6. (a) Cell of the seven-layer modulated martensite phase (14M) of an arbitrary composition sample seen in 3D and laterally. (b) Cell of the five-layer modulated martensite phase (10M) of an arbitrary composition sample seen in 3D and laterally (generated with MAUD-free software, version 2.08, Luca Lutterotti, Trento, Italy).
Figure 6. (a) Cell of the seven-layer modulated martensite phase (14M) of an arbitrary composition sample seen in 3D and laterally. (b) Cell of the five-layer modulated martensite phase (10M) of an arbitrary composition sample seen in 3D and laterally (generated with MAUD-free software, version 2.08, Luca Lutterotti, Trento, Italy).
Metals 13 00111 g006
Metals 13 00111 g007 550
Figure 7. Ductile-brittle diagram of some conventional Ni–Mn–Z (Z = Ga, Al, In and Sn) and stoichiometric Ni2MnTi alloys. The horizontal dashed and the vertical dashed dot lines indicate Pettifor’s and Pugh’s brittleness–ductility criteria, respectively. The inhibition of covalent p–d hybridization obtained by removing the p-group atom is supported by this result. Reproduced with permission from ref. [79]. Copyright 2019 Elsevier.
Figure 7. Ductile-brittle diagram of some conventional Ni–Mn–Z (Z = Ga, Al, In and Sn) and stoichiometric Ni2MnTi alloys. The horizontal dashed and the vertical dashed dot lines indicate Pettifor’s and Pugh’s brittleness–ductility criteria, respectively. The inhibition of covalent p–d hybridization obtained by removing the p-group atom is supported by this result. Reproduced with permission from ref. [79]. Copyright 2019 Elsevier.
Metals 13 00111 g007
Table
Table 1. Sites associated withX, Y, and Z atoms for the different austenitic phases of Heusler-type stoichiometry alloys.
Table 1. Sites associated withX, Y, and Z atoms for the different austenitic phases of Heusler-type stoichiometry alloys.
StructureX Atoms (Sites)Y Atoms (Sites)Z Atoms (Sites)
L21A, CBD
Inverse XAB, CAD
Disordered B2A, CB, DB, D
Disordered A2A, B, C, DA, B, C, DA, B, C, D
Table
Table 2. Young’s elastic modulus E for some representative conventional (p–d) and all-d-metal (d–d) Heusler alloys.
Table 2. Young’s elastic modulus E for some representative conventional (p–d) and all-d-metal (d–d) Heusler alloys.
CompositionNi2MnAlNi1.48Co0.52Mn1.4Ti0.6Ni2MnGa
Typep–dd–dp–d
E (Gpa)192.0054.81124.61
Refs.[39][40][41]
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Bachagha, T.; Suñol, J.-J. All-d-Metal Heusler Alloys: A Review. Metals 2023, 13, 111. https://doi.org/10.3390/met13010111

AMA Style

Bachagha T, Suñol J-J. All-d-Metal Heusler Alloys: A Review. Metals. 2023; 13(1):111. https://doi.org/10.3390/met13010111

Chicago/Turabian Style

Bachagha, Tarek, and Joan-Josep Suñol. 2023. "All-d-Metal Heusler Alloys: A Review" Metals 13, no. 1: 111. https://doi.org/10.3390/met13010111

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop