52 Journal of Solar Energy Research Updates, 2022, 9, 52-69

Magneto-Structural Transition and Refrigeration Property in All-D-

Metal Heusler Alloys: A Critical Review

Qinyu Zhang, Mingfang Qian* and Xuexi Zhang*

School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
Abstract: All-d-metal Heusler alloys has attracted much attention due to its unique magnetic properties, martensite
transformation behavior and related solid-state refrigeration performance. These unique type alloys are recently
discovered in 2015 and have been widely studied; however, systematic reviews on their magneto-structural transition
and refrigeration property are rare. In this review, we first summarize the preparation techniques and microstructure of
the bulk alloys and ribbons. Then the magnetic transition and martensite transformation behavior are reviewed, focusing
on the correlation between magneto-structural transition and refrigeration properties. The effects of element doping,
external magnetic and mechanical fields on the martensite transformation and corresponding magnetic entropy change
are summarized. We end this review by proposing the further development prospective in the field of all-d-metal Heusler
alloys.

Keywords: All-d-metal Heusler alloys, Microstructure, Magneto-structural transition, Magnetic properties, Magnetic
refrigeration.

1. INTRODUCTION contain d-group elements and thus are named all-d-

metal alloys, which show enhanced mechanical
Heusler alloys, first discovered by Fritz Heusler in properties and thus attracted much attention in recent
1903, have attracted much attention due to their unique years.
physical and chemical properties. Currently, Heusler-
type alloys are promising candidate materials for Up to now, great progress has been made in the
various fields, such as actuation [1], energy conversion field of all-d-metal Heusler alloy. However, critical
[2-4], refrigeration [5-12], catalysis [13, 14] and so on review on this field is still lack. In this brief review, we
[15-20]. first summarized the preparation methods and
microstructure of all-d-metal Heusler alloys. Then the
The element constituents and crystal structure of factors affecting the martensite/magnetic transitions
traditional Heusler alloys with X2YZ formula are shown and mechanical/magnetic/magnetocaloric properties
in Figure 1. In generally, X and Y are d-group transition were reviewed. Finally, the development prospective of
metal elements, while Z is p-group main elements all-d-metal Heusler alloys was provided.
[21-23]. Heusler alloys usually exhibit two different
crystal structures: Cu2MnAl-type (No. 225) and 2. PREPARATION AND MICROSTRUCTURE OF
Hg2CuTi-type (No. 216). The covalent bond formed via ALL-D-METAL ALLOYS
p-d orbital hybridization between p- and d-group atoms
may stabilize the parent phase [24]. On the other hand, Different methods have been employed to prepare
such covalent bond is prone to induce the poor different all-d-metal alloys [12, 41-55]. Meanwhile, their
mechanical properties (especially the low ductility), microstructures were characterized by a lot of
which greatly limited their practical applications [7, 11, technique, including optical microscopy (OM), scanning
25]. electron microscopy (SEM), electron backscattered
diffraction (EBSD) and transmission electron
A variety of approaches have been employed to microscopy (TEM).
improve the mechanical properties of Heusler alloys [7,
8, 26-40]. In 2015, Wei et al. [41] prepared a kind of All-d-metal bulk alloy ingots are usually prepared by
novel Heusler alloys by replacing p-group atoms with arc-melting under inert gas atmosphere. The
third transition metal atoms. The created alloys only microstructure of Ni40Cu10Mn35Ti15 and
Ni37Co13Mn34.5Ti15.5 alloy ingots is displayed in Figure 2
[42, 56]. The as-cast Ni40Cu10Mn35Ti15 alloy exhibited
typical cellular structure (Figure 2a), different with the
*Address correspondence to this author at the School of Materials Science and globular microstructure of the cast Ni37Co13Mn34.5Ti15.5
Engineering, Harbin Institute of Technology, Harbin 150001, China;
E-mail: mingfang.qian@hit.edu.cn, xxzhang@hit.edu.cn alloy (Figure 2c). The different microstructure was

E-ISSN: 2410-2199/22 © 2022 Zeal Press

Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 53

Figure 1: Constituents and structure of Heusler alloys [21]. (a) Element constituents; (b) Cu2MnAl-type structure; (c)
Hg2CuTi-type structure.

Figure 2: Microstructure of all-d-metal bulk alloys [42, 56]. (a) As-cast and (b) annealed Ni40Cu10Mn35Ti15, (c) As-cast and (d)
annealed Ni37Co13Mn34.5Ti15.5.

related to the different solidification rates. Compared annealed ribbons in Figure 3a and b shows that the
with the as-cast state, the annealed alloys (Figure 2b average grain size slightly increased after annealing,
and d) show better chemical homogeniety on the as illustrated in Figure 3c and d. Depicted in Figure 3e
microscopic scale, which is beneficial for the functional and f is the corresponding fracturing cross-section
properties of materials [41]. images of melt-spun and annealed ribbons, revealing
that columnar grains perpendicular to the free surface
All-d-metal alloy ribbons can be prepared by melt- are created.
spinning technique [47-53]. The typical microstructure
of Ni36.0Co14.0Mn35.7Ti14.3 ribbons is shown in Figure 3 On the other hand, all-d-metal Heusler alloys film
[49]. The martensite and equiaxed-grain-like austenite can be well prepared by direct-current (DC) double
can be observed on the free surface of the ribbon targets magnetron co-sputtering method [54, 55]. In
(Figure 3a), indicating that the martensite this technique, the MgO (100) substrate was often
transformation (MT) of the ribbon takes place at used. Figure 4 demonstrates the typical
ambient temperature. Comparison of the melt-spun and microstructures of Ni-Co-Mn-Ti all-d-metal Heusler
54 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Figure 3: Microstructures of all-d-metal Ni36.0Co14.0Mn35.7Ti14.3 alloy ribbons. (a,c) Free surfaces of melt-spun ribbons; (b,d) Free
surfaces of annealed ribbons; (e) Cross sections of melt-spun ribbons; (f) Cross sections of annealed ribbons. Free surface: free
solidification side surface far away from copper roller [49].

alloys film [55]. From the surface images, the

agglomeration and contrast among particles indicate
that the films grow in island mode (Volmer-Weber
mode), in which the grains produce different heights. It
is obvious that the average grain size increases with
increasing deposition temperature (DT). The average
grain size for Ni40.5Co14.1Mn31.6Ti13.8 (sample A),
Ni40.6Co14.1Mn31.5Ti13.8 (sample C), and
Ni39.3Co15.3Mn31.8Ti13.6 (sample D) are about 21.5(6) nm,
36.5(1) nm and 85.5(0) nm, respectively. In addition, a
lot of small grains are also observed in Figure 4c and
e. These small grains may be formed by pure Ni, Co,
Mn or Ti elements, implying that the Ar ions on the
surface may possibly hinder the diffusion of sputtered
atoms on the surface. From the fracture cross-section
of films (Figure 4b, d and f), sample A, C and D have a
thickness of ∼620, ∼670 and ∼700 nm, respectively.
This shows that the film thickness slightly increase with
the increasing DT.

3. MAGNETO-STRUCTURAL TRANSITION AND Figure 4: SEM images showing the surfaces and cross
PROPERTIES OF ALL-D-METAL ALLOYS sections for (a, b) Ni40.5Co14.1Mn31.6Ti13.8 (sample A), (c, d)
Ni40.6Co14.1Mn31.5Ti13.8 (sample C) and (e, f)
All-d-metal Heusler alloys have many fascinating Ni39.3Co15.3Mn31.8Ti13.6 (sample D). The grain size increases
with increasing DT. The cross-section images show the
multifunctional properties, which are related to the MT
thickness is almost the same for all samples, indicating that
from high-temperature austenite to low-temperature DT has little effect on the thickness of the films [55].
martensite phases [48-51, 53-55, 57, 58]. Therefore,
the factors affecting the MT play an important role in Wei et al. [41] prepared the Ni50Mn50-yTiy (y = 0, 6, 9,
the properties and applications of all-d-metal Heusler 12, 15, 20, 25, 30, denoted as Tiy) and Mn50Ni50-yTiy (y
alloys. = 0, 6, 9, 10, 11, 12, 15) alloys by arc-melting high
purity metals in argon atmosphere. In Figure 5a, the
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 55

Figure 5: Phase and magnetic properties of Ni50Mn50-yTiy (y = 0, 6, 9, 12, 15, 20, 25, 30) alloys. (a) Room-temperature X-ray
diffraction (XRD) patterns at ambient temperature; (b) Temperature dependent magnetization (M-T) curves for Ni50Mn50-yTiy (y =
-1
20, 25, 30) alloys and M -T plot for Ti20. The left inset in (b) shows the differential scanning calorimetry (DSC) result for
Ni50Mn35Ti15 alloy, and the right inset in (b) is the magnetic isotherms of Ti20 at temperatures well above and below TM. Ms and
Mf refer to the starting and finishing temperatures of forward MT, respectively. As and Af are the starting and finishing
temperatures of inverse MT, respectively [41].

L10 martensite phase exists in the low-Ti-content alloys 3.1. Element Doping
(Ti0, Ti6 and Ti9) at room temperature (RT), only
austenite phase is observed for high-Ti-content alloys (1) Magnetic element doping. The strong
(Ti20, Ti25 and Ti30). Coexistence of different ferromagnetism was not established by introducing Ti
martensite phases (L10 and 5M) exists in medium-Ti- in the Ni-Mn-Ti and Mn-Ni-Ti all-d-metal Heusler alloys.
content alloys (Ti12 and Ti15). The MT temperature of Wei et al. [41, 43] applied the “ferromagnetic (FM)
Ni50Mn50-yTiy alloys decreases with increasing Ti activation effect” of the Co atom to induce the
content. For Ti20 (Figure 5b), the thermal hysteresis of ferromagnetic transition in Ni-Mn-Ti and Mn-Ni-Ti
181-194 K is observed. Meanwhile, the fact that a alloys. The abrupt magnetic transitions corresponding
-1
linear fit of M -T above the MT with a negative to MT from strong FM austenite to weak-magnetic (PM
or AFM) martensite can be seen in Figure 6. It shows
extrapolated temperature confirms the
that metamagnetic martensite transformation exists in
antiferromagnetic (AFM) character of the austenite.
Co-doped Ni-Mn-Ti and Mn-Ni-Ti alloys.
The linear magnetic isotherms at temperature of 200 K
(austenite) and 150 K (martensite) (right inset of Figure 7 demonstrates the magnetic and magneto-
Figure 5b) indicate paramagnetic (PM) behavior of the responsive properties across the MT of a
austenite and FM behavior of the martensite, Ni35Co15Mn35Ti15 alloy [41]. A large magnetization
respectively This type of magneto-structural MT -1
difference (ΔM) about 90 emu g is associated with MT
between high- and low-temperature PM phases differs transformation (Figure 7a), which facilitates
significantly from the first-order magnetic transition transformation-related magneto-responsive effects.
(FOMT) in some other materials, such as Gd-Si-Ge Magnetic isotherms across the MT are shown in Figure
[55]. 7b. At 290 K, the austenite reveals typical FM behavior.
The isotherms at lower temperatures of 235, 253 and
Currently, the main factors affecting the actual 270 K exhibit a clear metamagnetic behavior (i.e.
applications of all-d-metal alloys are low mechanical magnetic-field induced reverse MT from weak-
toughness and limited functional properties, partially magnetic martensite to strong-ferromagnetic austenite)
related to defects during fabrication [41, 43]. Some with pronounced magnetic hysteresis. Especially, at
strategies have been proposed to overcome these 253 K a two-way reversible MT is observed. Figure 7c
problems, including (a) element doping, (b) shows the field dependence of the strain. At 253 K, the
microstructure adjustment (texture and reducing strain saturates with a maximum value of 2400 ppm in
sample size) and (c) multi-field cooperation. Of course, a magnetic field of 120 kOe. This large magneto-strain
researches could apply these strategies based on originates from cell volume expansion due to the field-
actual demands. induced reverse MT. The strain recovery during
decrease of the field indicates magnetic superelasticity
56 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Figure 6: M-T curves of (a) Ni50-xCoxMn35Ti15, (b) Mn50Ni40-xCoxTi10 alloys [41, 43].

Figure 7: Magnetic and magneto-responsive properties across the MT of the Ni35Co15Mn35Ti15 alloy. (a) Temperature
dependence of the magnetization in magnetic fields of 0.1 and 120 kOe; (b) Magnetic isotherms at several temperatures; (c)
Field-induced strain at several temperatures. The inset shows the temperature dependence of the strain; (d) Magnetic-entropy
change (ΔSm) at various field changes. The inset shows the refrigerating capacity (RC); (e) Temperature dependence of the
electrical resistivity in magnetic fields of 0, 70, and 120 kOe. The inset shows the temperature dependence of the
magnetoresistance (MR); (f) Field dependence of the MR at various temperatures [41].

of the alloy. The magnetic entropy changes (ΔSm) were distortion. A remarkable shift of the jump onset with
calculated using Maxwell relation, as shown in Figure increasing field towards lower temperatures is related
-1 -1
7d. A maximum ΔSm value around 18 J kg K is to the field-induced FMMT. As illustrated in the inset of
obtained at about 263 K under a field change of 50 Figure 7e, large magnetoresistance (MR) values of
kOe. The obtained ΔSm is comparable to that of many 37% at 70 kOe and 46% at 120 kOe are found across
other Heusler alloys. The inset of Figure 7d shows the MT. The field dependent MR at different temperatures
refrigeration capacity (RC), which has a relatively high is shown in Figure 7f, which is consistent with the field
-1
value of 267 J kg under 50 kOe. This shows that the dependence of the strain.
Co-doped all-d-metal Heusler FSMAs may have a
potential as magnetocaloric materials. (2) Cu doping. De Paula et al. [56] prepared the
Ni40Cu10Mn35Ti15 alloy and investigated its magnetic,
The MT is accompanied by an electrical resistance electronic, and mechanical properties after thermal
change. To investigate this effect, the temperature annealing. Compared with Ni50Mn35Ti15 in the inset of
dependence of the electrical resistance was measured Figure 5b, it was observed that the MT temperature of
in various magnetic fields, as shown in Figure 7e. The Ni40Cu10Mn35Ti15 decreased due to the doping of Cu
electrical resistance exhibits abrupt jump across the (inset of Figure 8a). In Figure 8a, an antiferromagnetic
FMMT due to intrinsic changes of both the anisotropy ordering transition with large thermal hysteresis takes
and the area of the Fermi surface caused by the lattice place for both the annealed and as-cast samples,
suggesting the presence of MT in this alloy. The
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 57

magnetic phase transition from the paramagnetic to the (3) B doping. Boron element was usually used to
antiferromagnetic state is also strongly correlated with enhance the grain boundary strength and thus improve
the electric resistivity. Figure 8b shows abrupt increase the mechanical properties [12, 46]. Cong et al. [46]
in resistivity values in both samples as temperature synthesized (Ni50Mn31.5Ti18.5)99.8B0.2 alloys and
decreases below 154 K. In fact, the sharp increase in investigated its elastocaloric effect (eCE) and crystal
electrical resistivity across the MT is a common feature structure. Micro-alloying with B leads to decreasing
in conventional Ni-Mn-based Heusler alloys. This
transformation temperature in Figure 9a. Figure 9b
feature is attributed to the changes in the atomic bond
shows that the MT of (Ni50Mn31.5Ti18.5)99.8B0.2 alloy
length of Ni and Mn atoms due to symmetry reduction
occurs between paramagnetic austenite and
across MT, which alters the density of states near the
Fermi level. In addition, no cracks appear at the paramagnetic martensite. The adiabatic temperature
indentation corners of the annealed Ni40Co10Mn35Ti15 change (ΔTad) and isothermal entropy change (ΔSiso)
samples after Vickers micro-hardness indentation are two important parameters for eCE. The ΔTad
(Figure 8b), revealing that the sample may possibly (Figure 9c) and ΔSiso (Figure 9d) are 31.5 K and 45 J
-1 -1
has good toughness. kg K , respectively. To better understand the colossal

Figure 8: Magnetization properties and indentation of Ni40Cu 10Mn35Ti15 alloys [56]. (a) DC magnetic susceptibility of as-cast and
annealed alloys, following ZFC/FC protocols under the applied magnetic field of 1 kOe. The inset is the MT temperatures at 10
kOe for the annealed alloy; (b) Temperature dependence of DC electrical resistivity of the As-cast and annealed alloys; (c)
SEM-BSE images showing the micro-hardness indentation.

Figure 9: Phase transitions of boron-microalloyed (Ni50Mn31.5Ti18.5)100-xBx alloys [46]. (a) DSC curves of (Ni50Mn31.5Ti18.5)100-xBx
alloys; (b) M-T curves of (Ni50Mn31.5Ti18.5)99.8B0.2 alloy under constant magnetic fields of 0.05, 1 and 5 T; (c) Colossal adiabatic
temperature change in (Ni50Mn31.5Ti18.5)99.8B0.2 alloy; (d) Isothermal entropy change as a function of temperature at different
strain levels; (e) Crystal structure evolution during stress-induced transformation in (Ni50Mn31.5Ti18.5)99.8B0.2. (Left) 1D HEXRD
patterns at different stress levels during loading and unloading at 295 K. (Right) Representative zone of the 2D HEXRD patterns
collected before loading (2 MPa), at the maximum stress (490 MPa), and after unloading (1 MPa) at 295 K.
58 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

eCE and its underlying mechanism, an in-situ critical temperatures of MT (Figure 10a), i.e., Ms, Mf, As
synchrotron HEXRD experiment was performed to and Af, were determined by tangent method to be
trace the structural evolution during loading and 254.8, 225.7, 240.1 and 272.2 K, respectively. The
unloading processes. As displayed in Figure 9e, the thermal hysteresis ΔTHys (i.e. [(As  +  Af)  −  (Ms  +  Mf)]  /  2)
sample exhibits austenite structure (No. 225) before and phase transition interval ΔTInt (i.e.
loading. Upon applying an external stress, it transforms [(Ms  −  Mf)  +  ( Af  −  As)]  /  2) that describe the reversibility of
into an orthorhombic (No. 51) martensite. Notably, the structural transition, are 15.9 and 30.6  K, respectively.
stress-induced MT is fully accomplished when the Figure 10b shows similar results in Ni50Mn50-yTiy and
stress reaches 413 MPa. During unloading, the stress- Mn50Ni50-yTiy alloys, which exhibit MT between
induced martensite fully transforms back to austenite. paramagnetic austenite and paramagnetic martensite.
2D HEXRD patterns (right of Figure 9e) collected Figure 10c shows the time dependence of ΔTad with an
before and after loading are almost identical, indicating applied strain of 10%. A giant ΔTad of −20.4  K is
that the stress-induced transformation is fully detected during reverse MT. In Figure 10d, the ultimate
reversible. The good reversibility of the stress-induced compressive strain and stress of the <100>-­‐textured
transformation is important for colossal reversible eCE. Ni50Mn31.75Ti18.25 alloy are determined to be ~13% and
Aznar et al. [12] also prepared (Ni50Mn31.5Ti18.5)99.8B0.2 ~1.1  GPa, respectively. As a result of the existence of
alloys with giant barocaloric effect (BCE), which shows texture structure, the alloy shows largely enhanced
-1 -1
ΔTad and ΔSiso of 12 K and 74 J kg K , respectively. fracture resistance in comparison with that of
conventional Ni-Mn-based alloys [30, 59-62].
3.2. Introduction of Texture During Fabrication
3.3. Combination of Doping and Reducing Material
Texture structure was usually used to improve the Size
mechanical properties [36]. Yan et al. [44] fabricated
<100>-­‐textured Ni50Mn31.75Ti18.25 bulk alloy by arc- Liu et al. [48] prepared the all-d-metal Ni50-
melting and directionally solidification technique. The x Co xMn35Ti15 (x  =  1 3,13.5) ferromagnetic alloy ribbons

Figure 10: Martensite transformation, magnetic and mechanical properties of Ni50Mn31.75Ti18.25 alloy. (a) DSC curve of
directionally solidified alloy with <100>-­‐texture; (b) M-T curves of under magnetic fields of 0.01 and 1  T; (c) Time dependence of
ΔTad in the sample with an applied strain of 10%; (d) Comparison of the fracture curves of the <100>-­‐textured Ni50Mn31.75Ti18.25
alloy with that of the conventional Ni-Mn-based alloys. “DS” and “P” represent the directionally solidified and the casted
polycrystalline samples, respectively. The inset is the fracture surface of the studied alloy [44].
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 59

via arc-melting and subsequent melt-spinning manifests the excellent mechanical properties of the
techniques under Ar atmosphere. The phase transition annealed ribbon in contrast to some steel materials
and correlative properties of ribbon samples were [63-65].
investigated. Compared to the structure (only B2-type)
of melt-spun ribbon at RT, Figure 11a shows the Neves Bez et al. [50] found that the peak value of
coexistence of three different phases (L10, 5M, B2) in ΔSm decreases with increasing Co content in the Ni50-
the annealed Ni36.5Co13.5Mn35Ti15 ribbons, implying that xCoxMn35Ti15 (12.5<x  <15) alloy ribbon (Figure 12a).

the intermartensite transformation (IMT) exists and MT More interestingly, the ΔSm of the Ni37.5Co12.5Mn35Ti15
shifts markedly to higher temperatures after annealing ribbon is 400% higher than that of the bulk alloy (Figure
12b). The enhanced ΔSm may be attributed to the
at 850  °C. The critical temperatures of MT in annealed
presence of high degree of chemical homogeneity in
Ni36.5Co13.5Mn35Ti15 alloy ribbon (Figure 11b), i.e., Ms,
the ribbon. Zeng et al. [53] fabricated the Ni50-
Mf, as and Af, are determined to be 306.5, 284, 8,
xFexMn35Ti15 alloy ribbons by introducing Fe element in
311.6 and 327.2 K, respectively. The thermal
Ni-Mn-Ti alloy and discussed the effect of Fe element
hysteresis ΔTHys and phase transition interval ΔTInt are
on MT. The XRD (Figure 13a) and DSC (Figure 13b)
23.8 and 32.6  K, respectively. Figure 11c shows M-T
indicate that Fe substitution efficiently decreases the
curves of annealed ribbon under applied fields µ0H of
transformation temperature by stabilizing the B2 parent
0.1 and 5  T. With further decreasing temperature, an
phase. For Ni32Fe18Mn35Ti15 alloy ribbon, the
abrupt drop of magnetization indicates the occurrence
transformation temperatures of the forward and reverse
of MT from FM parent phase to weak-magnetic
MT are determined to be 192 and 208  K, respectively.
martensite. Meanwhile, the increase in applied filed Figure 13c shows that FMMT has been realized in
from µ0H = 0.1-5 T leads to the shifts of MT to lower Ni32Fe18Mn35Ti15 alloy ribbon. The role of Fe element is
temperatures. Under the applied fields µ0H of 5  T similar to that of Co element. Under an applied field
during reverse MT, the ΔM (Figure 11c), ΔSm (Figure µ0H of 5  T during reverse MT, the ΔM (Figure 13c) and
2 -1
11d) and RC (inset of Figure 11d) are 86.9 Am kg , ΔSm (Figure 13d) of Ni32Fe18Mn35Ti15 alloy ribbon are
-1 -1 -1
24.9 J kg K and 239.7 J kg , respectively. As 2 -1 -1 -1
35 Am kg and 12.5 J kg K , respectively. The MR
illustrated in Figure 11e, quite large MR value of 34.9% (Figure 13e) and anomalous Hall effect (Figure 13f) are
at 5T is found across the transformation. Figure 11f observed across the transformation. Li et al. [51]

Figure 11: Phase transition, magnetic property and properties of Ni36.5Co13.5Mn35Ti15 alloy ribbons [48]. (a) Room-temperature
XRD patterns for melt-spun and annealed (at 850 ℃) ribbons; (b) DSC curves for annealed ribbon; (c) M-T curves of annealed
ribbon under applied fields µ0H of 0.1 and 5  T; (d) ΔSm (T) curves of annealed ribbon under different field changes Δµ0H   of 0-1,
2, 3, 4, 5  T. The corresponding insets show the magnetic field change dependence of RC; (e) Magnetoresistance of annealed
ribbon under magnetic field change Δµ0H  0 -5 T; (f) Vickers hardness of annealed ribbon and some other well-studied steels.
60 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Figure 12: Magnetic entropy change of Ni37.5Co12.5Mn35Ti15 ribbons [50]. (a) Temperature dependence of ΔSm; (b) ΔSm of
Ni37.5Co12.5Mn35Ti15 ribbons and bulk alloys under various magnetic field changes.

Figure 13: Microstructure and properties of Ni50−xFexMn35Ti15 (denoted as Fex) ribbons [53]. (a) Room temperature XRD
patterns; (b) DSC measurements for the MT. The insert shows hysteresis (ΔT) dependence on Fe content and latent heat (ΔH)
obtained from DSC; (c) M-T curves of Fe18 sample under different magnetic fields; (d) Temperature dependence of the
magnetic entropy changes (ΔSm) with magnetic fields 10-90 kOe; (e) Magnetic field dependence of MR at various temperatures
of Fe18. The insert is the temperature dependence MR under a magnetic field of 70 kOe; (f) Magnetic field dependence of Hall
resistivity ρxy at various temperatures of Fe18. The insert is the temperature dependence of ρxy in 70 kOe.

investigated the influence of different Co/Fe ratio on the Figure 14b. As shown in the top right-hand corner of
crystal structure, FMMT and magnetocaloric effect Figure 14b, the magnetization of FM austenite
(MCE) of Ni35Co15−xFexMn35Ti15 (x  =  2, 4, 6, 8) alloy decreases and Tt increases with decreasing Co/Fe
ribbons. ratio. In all as-prepared ribbons, the Ni35Co9Fe6Mn35Ti15
ribbon shows the highest ΔSM and RC. Under magnetic
All the Ni35Co15−xFexMn35Ti15 alloys exhibit B2-type
fields of 20 and 50  kOe during reverse MT, the
cubic structure at RT (Figure 14a), indicating that the
maximum values of ΔSM/RC reach 9.5(8)
temperature of MT is lower than RT. An abrupt −1 −1 −1 −1 −1
J  kg   K /79.4(5) J  kg and 24.0(4) J  kg   K /206.8(4)
magneto-structural transformation (MST) occurs from −1
J  kg , respectively. Huang et al. [47] studied the effect
strong FM austenite to weak magnetic martensite for
of rare earth Y doping on the crystal structure, MT and
Ni35Co15−xFexMn35Ti15 (x  =  2, 4, 6, 8) alloy ribbons in
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 61

MCE of Mn50-x YxNi30.5Co9.5Ti10 (x = 0, 0.3, 0.5, 0.7) rare earth Y-precipitation phase (Figure 15d). The ΔSm
ribbons. Compared with the microstructure of increased with increasing rare earth Y. The maximum
Mn50Ni30.5Co9.5Ti10 ribbon (Figure 15a) at RT, little ΔSm of Mn49.3Y0.7Ni30.5Co9.5Ti10 ribbons (Figure 15e)
-1 -1
secondary phase (red arrow) randomly distributing in reaches 6.16 (23.7) J kg K under 20 (70) kOe.
B2 phase is observed in Mn49.3Y0.7Ni30.5Co9.5Ti10
ribbons (Figure 15b). Figure 15c shows that the 3.4. Combination of Doping and Texture
sample exhibits B2 and 5 M phases for x = 0, and main
Shen et al. [66] studied the <001>-oriented
B2 phase with the increase of rare earth Y. At the same
Ni35.5Co14.5Mn35Ti15 polycrystals prepared by arc-
time, the MT temperature from ferro- to weak-magnetic
melting and directionally solidification technique. In
state monotonously declines due to the enrichment of

Figure 14: Phase, magnetization and magnetocaloric effect (MCE) of Ni35Co15−xFexMn35Ti15 ribbons [51]. (a) Room temperature
XRD patterns. The inset is the crystal structure and atomic site occupations; (b) M-T curves under a field of 1  kOe. The
A
corresponding values of MT temperature (Tt) and Curie temperature of austenite (TC ) for samples were displayed; (c) The
magnetic entropy change ΔSM as a function of temperature around reverse MT temperature with magnetic fields 10-70 kOe.

Figure 15: Microstructure, magnetic property and magenetocaloric effects of Mn50-xYxNi30.5Co9.5Ti10 (x = 0, 0.7) alloy ribbons
[47]. (a, b) Microstructure on the free surface; (c) XRD patterns at RT; (d) Temperature dependence of magnetization under a
magnetic field of 0.1 kOe; (e) Magnetic entropy change (ΔSm).
62 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Figure 16a, Ms, Mf, As, Af and ΔTHys of samples are texture is favorable for improving the eCE performance.
292.9, 278.8, 290.8, 301.4 and 10.2 K, respectively. Wei et al. [67] use the same method to prepare the
Meanwhile, the corresponding thermal-induced MT <001>-oriented Ni35.5Co14.5Mn35Ti15 polycrystals. The
entropy change (ΔST) could be evaluated to be 42.1 J as-prepared specimen exhibits large barocaloric effect
-1 -1 −1 −1
g K . Their MT behaviors (Figure 16b) are similar to with a ΔSm of −24.2 J kg K and an ΔTad of 4.2 K by
that of previously reported non-textured Ni-Co-Mn-Ti the application of a relatively low pressure of 1 kbar.
alloys [57]. The value of ΔM under a magnetic field of
-1 3.5. Combination of Doping and Multiple External
50 kOe reaches 94 emu g . Figure 16c shows that the
Fields
specimen subjects to MT at a rather low critical stress
(σcr) of 38 MPa, which produces a transformation strain The applying of multiple external fields may
(Δεtr) of 4%. To complete MT, the applied stress of effectively enhance the RC of Heusler alloys [7, 68-70].
about 110 MPa is required since MT is not a strictly Liu et al. [45] studied the effect of hydrostatic pressure
equilibrium process due to unavoidable nucleation on MCE of Ni37.5Co12.5Mn35Ti15 bulk alloy. The
process [7]. The stress hysteresis (Δσhy) is 54 MPa due magneto-structural phase transition process is shown
to the fact that ambient temperature is close to Af, in Figure 17a. Meanwhile, the magnetic field reduces
leading to a low thermal driving force for the reverse -1
TM temperatures with a rate of -1.4 K T . Moreover,
MT. For the loading and unloading stages (Figure 16d), the reduction of ΔM across the martensitic transition is
ΔTad of 11.5 K and 5.8 K can be obtained. Such an observed under hydrostatic pressure (Figure 17b). At
asymmetry in |∆Tad| suggests the irreversibility of the ambient pressure, ΔM reaches 81.3 emu g at 7 T
-1

eCE between the forward and reverse MT. The main under a 10.03 kbar hydrostatic pressure, then it
source of the irreversibility is ascribed to the dissipative -1
decreases to 54.4 emu g . It means that reduction of
heat of internal friction caused by the fast interfacial maximum ΔSM of Ni37.5Co12.5Mn35Ti15 bulk alloy exist
movement upon fast loading/unloading. Compared with under the hydrostatic pressure. The ΔM peak shifts
other reported first-order elastocaloric materials (Figure continuously to a higher temperature with increasing
16e), the <001>-oriented Ni35.5Co14.5Mn35Ti15 hydrostatic pressure. With the application of multi-
polycrystalline alloys display excellent eCE. In addition, fields, i.e. first applying a magnetic field and
the results (Figure 16f) proved that the existence of withdrawing magnetic field under a hydrostatic

Figure 16: Phase transition, elastocaloric and magnetocaloric effect of polycrystalline Ni35.5Co14.5Mn35Ti15 alloys [66]. (a) DSC
curves of <001>-textured alloys; (b) M-T curves under applied fields (µ0H) of 0.1 and 5  T; (c) Stress-strain curve of sample at a
strain rate of 0.1 mm/min at 310 K; (d) Temperature-time profile; (e) Specific adiabatic temperature change vs critical stress
(|ΔTad/σcr|) and transformation strain (|ΔTad/Δεtr|); (f) Stress hysteresis (Δσhy) for typical room-temperature elastocaloric
materials.
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 63

Figure 17: Magnetic properties and magnetocaloric effect of Ni37.5Co12.5Mn35Ti15 bulk alloy [45]. (a) The Iso-field magnetization
curves measure at ambient pressure with magnetic fields 0.01, 2 and 7 T; (b) Iso-field magnetization curves measure at fixed
magnetic field 7 T under hydrostatic pressures 0, 1.43, 2.67, 6.4, and 10.03 kbar; (c) Heating ΔS-T curves under ambient
pressure and cooling ΔS-T curve under hydrostatic pressure of 1.43 kbar under magnetic field changes of 0.01 to 5 T.

A
pressure, the reversible entropy change increases from increasing Fe content, the TC increases while Tt
−1 −1
8.9 to 24.1 J kg K (Figure 17c) for a magnetic field obviously decreases. Figure 18b shows the reduction
change from 0.01 to 5 T. of ΔM across the martensitic transition with increasing
hydrostatic pressure from 0.25 to 0.75 GPa; the Tt also
3.6. Combination of Doping, Reducing Sample Size increases with increasing hydrostatic pressure. These
and Multiple External Fields results (Figure 18b) are similar to that of previously
reported Ni-Co-Mn-Ti bulk alloys [45]. In
Li et al. [52] applied the hydrostatic pressures in
Ni35Co15Mn31Fe4Ti15 Heusler ribbon, the ΔM (67.09
Ni35Co15Mn35−xFexTi15 ribbons and systematically -1
emu g ) under ambient pressure is lower than that
investigated the phase transition and magnetocaloric
under different hydrostatic pressures. By contrast, the
performance. All the samples (Figure 18a) exhibit -1
ΔM (81.3 emu g ) of sample under ambient pressure is
magneto-structural phase transition behavior. With

Figure 18: Magnetic properties, phase transition and magnetocaloric effect of Ni35Co15Mn35−xFexTi15 (x = 2, 4, 6) ribbons [52].
(a) M-T curves under a magnetic field of 1 kOe; (b) M-T curves for Ni35Co15Mn31Fe4Ti15 ribbon under a magnetic field of 1 kOe
and hydrostatic pressures of 0, 0.25, 0.35 and 0.72 GPa; (c) Phase diagrams of (c1) Ni35Co15Mn35−xFexTi15 (x = 2, 4, 6) ribbons
and (c2) Ni35Co15Mn31Fe4Ti15 ribbon under hydrostatic pressures of 0, 0.25, 0.35 and 0.72 GPa; (d) ΔSM as a function of
hydrostatic pressure with magnetic field changes of 10, 20, and 50 kOe; (e) Magnetic field dependence of RC with temperatures
at full width half-maximum (FWHM) of ΔSM peaks under hydrostatic pressure.
64 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Figure 19: Microstructure and properties of Mn52.6Ni30.5Co7.8Ti9.1 composites combined with alloy ribbons, polyvinyl alcohol
(PVA) and polyethylene terephthalate (PET) [71]. (a) The demonstration of preparation schematic diagram; (b) SEM images of
the cross section for the Mn52.6Ni30.5Co7.8Ti9.1/PVA/PET composite; (c) XRD pattern for the Mn52.6Ni30.5Co7.8Ti9.1 ribbon; (d) DSC
curves for the Mn52.6Ni30.5Co7.8Ti9.1 ribbon; (e) The M-T curves for the Mn52.6Ni30.5Co7.8Ti9.1/PVA/PET composite under different
magnetic fields; (f) The M-T curves for the Mn52.6Ni30.5Co7.8Ti9.1/PVA/PET composite in tensile strain state (ε  =  6.0%) under
different magnetic fields; (g) The M-T curves for the Mn52.6Ni30.5Co7.8Ti9.1/PVA/PET composite in compressive strain states (ε  =  -
6.0%) under different magnetic fields; (h) The temperature dependence of isothermal magnetic entropy change (∆SM) for the
Mn52.6Ni30.5Co7.8Ti9.1 ribbon with the variation of the magnetic field from 0 to 5  T under different strain states.

higher than that under hydrostatic pressure in temperature of ribbons is around RT. In Figure 19d, the
Ni37.5Co12.5Mn35Ti15 bulk alloy. This may be attributed to related temperatures of MT (Ms, Mf, As and Af) are
the composition and microstructure difference of the 309.8  K, 276.2  K, 327.9  K and 351.9  K, respectively. On
ribbon and bulk alloys. In Figure 18c, the combined the other hand, the ΔTHys and ΔTInt are calculated to be
doping and hydrostatic pressures change the MST of 46.9 and 28.5  K, respectively. Figure 19e-g show the
all-d-metal alloys, shifting the MST to the desired different ΔM across the martensitic transition in
temperature rang. As depicted in Figure 18d and e, the different strain states at a magnetic field of 5  T.
-1
Ni35Co15Mn31Fe4Ti15 ribbon exhibits the best Compared with the ΔM (75.4 emu g ) under zero strain
magnetocaloric performance under hydrostatic (ε  =  0), the ΔM under higher strain (ε  = 6.0%) is
pressures of 0.35 GPa. The maximum values of ΔSM obviously higher. The peak of ΔSM (Figure 19h) under
−1 −1 −1 −1 −1
(RC) are 15.61 J kg K (109.91 J kg ) and 24.2 J 5  T is 12.44, 16.34 and 10.48  J  kg K at strains (ε) of
−1 −1 −1
kg K (347.26 J kg ) under 20 and 50 kOe,   0%, 6.0% and -6.0%, respectively. At the same time,
respectively. Zhao et al. [71] fabricated novel flexible the maximum RC obtained at three different strains (ε)
composites (Figure 19a) by combining of   0%, 6.0% and -6.0% is 157.02, 197.35 and 109.12  J
-1
Mn52.6Ni30.5Co7.8Ti9.1 ribbons, polyvinyl alcohol (PVA) kg , respectively.
and polyethylene terephthalate (PET). Figure 19b
clearly reveals the compact contact interfaces of Mn- 4. SUMMARY AND PERSPECTIVES
Ni-Co-Ti/PVA/PET flexible composite. The two-phase
The traditional Heusler alloys dispaly poor
coexistence of B2-type and five-layer modulated (5  M)
structure (Figure 19c) indicates that the MT mechanical properties (especially low ductility) due to
Magneto-Structural Transition and Refrigeration Property in All-D-Metal Heusler Alloys Journal of Solar Energy Research Updates, 2022, Vol. 9 65

the existence of covalent bond formed via p-d orbital size, which may effectively enhance the reversibility
hybridization in the parent phase. In order to overcome during solid state refrigeration cycling. The small-sized
the drawback of traditional Heusler alloys and improve materials may also act as building-blocks for complex
their practical applications, Wei et al. firstly prepared a shaped structures used for solid-state refrigeration, in
novel Heusler alloy (Ni-Mn-Ti, named all-d-metal which the large specific surface area of small-size
Heusler alloy) by only transition metal elements in materials improve the heat exchange capacity between
2015; it exhabited great mechanical properties because the working material and flowing reagent.
of the replacement of strong p-d hybridization by
relatively weaker d-d hybridization in Ni-Mn-Ti Heusler (c) Elastocaloric effect, driving by external
alloy. Meanwhile, the Ni-Mn-Ti all-d-metal Heusler alloy mechanical stress, may be promising for all-d-metal
showed large transition entropy changes and large alloys, supposing that these alloys exhibit high enough
volume changes across the martensitic transition. strength as well as ductility. Systematic studies on the
These features resulted in miraculously mechano- toughening mechanisms of these alloys become
caloric effects of Ni-Mn-Ti Heusler alloy. Unfortunately, necessary. On the other hand, the combination of
there were still some defects affecting the actual magnetocaloric and elastocaloric effects is also
applications of Ni-Mn-Ti or Mn-Ni-Ti all-d-metal alloys. important for their application for room-temperature
Researchers have invested great effort and employed refrigeration.
some strategies to solve these problems, including (a)
LIST OF ABBREVIATIONS
element doping, (b) microstructure adjustment (texture
and reducing sample size) and (c) multi-field MCE magnetocaloric effect
cooperation. All studies of all-d-metal alloys
eCE elastocaloric effect
demonstrated that they may act as promising
candidate materials for solid state refrigeration at BCE barocaloric effect
ambient temperature. However, the present studies MR magnetoresistance
mainly focused on the bulk state, and few works on MT martensite transformation
small-sized ribbons. In addition, most of the works
FMMT ferromagnetic martensite transformation
concentrate on the magnetocaloric effects rather than
FOMT first-order magnetic transition
elastocaloric effect. Finally, the mechanical properties
(especially the ductility enhancement and related IMT intermartensite transformation
mechanisms), have not been systematically MST magneto-structural transformation
investigated. AFM antiferromagnetic

Future research perspectives on all-d-metal Heusler PM paramagnetic

alloys lie on optimization of the composition, FM ferromagnetic
microstructure and preparation techniques. The Ms the starting temperatures of forward MT
corresponding properties, including mechanical,
Mf the finishing temperatures of forward MT
magnetic and refrigeration performance are crucial for
their critical applications. These include: As the starting temperatures of inverse MT
Af the finishing temperatures of inverse MT
(a) Compositional optimization, based on the
Tt temperature of MT
mechanical, magnetic, martensite transformation and A
TC Curie temperature of austenite
related properties, is necessary for the enrichment of
the alloy system. Some new design techniques such as ΔH latent heat
computational simulation combined with high ΔM magnetization difference
throughput experimental method may be promising; ΔSm magnetic entropy changes

(b) Preparation and properties of small sized ΔTad adiabatic temperature change
materials including wires, films and powders may ΔSiso isothermal entropy change
render all-d-metal alloys new advantages for new ΔTHys thermal hysteresis
properties and also applications. The magnetic
ΔTInt phase transition interval
hysteresis may be reduced via reducing the materials
ε strains
66 Journal of Solar Energy Research Updates, 2022, Vol. 9 Zhang et al.

Δεtr transformation strain combined with large elastocaloric and magnetocaloric

effects, Acta Materialia 221 (2021) 117390.
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W. Cai, Defect engineering: electron-exchange integral
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Ni41Mn43Co6Sn10 alloys, ACS Applied Materials &
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PET polyethylene terephthalate https://doi.org/10.1021/acsami.1c18587
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Yang, H.L. Yan, D.Y. Cong, X. Zhao, L. Zuo, Giant
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ACKNOWLEDGEMENT large lattice volume change upon the martensitic
transformation, ACS Applied Materials & Interfaces 14 (1)
(2022) 1505-1518.
Financial supports from Guangdong Province Key https://doi.org/10.1021/acsami.1c22235
Area R&D Program (Grant Number 2019B010942001) [11] Y. Li, W. Sun, D.W. Zhao, H. Xu, J. Liu, An 8 K elastocaloric
and Heilongjiang Touyan Team are greatly temperature change induced by 1.3% transformation strain in
acknowledged. Ni44Mn45-xSn11Cux alloys, Scripta Materialia 130 (2017)
278-282.
https://doi.org/10.1016/j.scriptamat.2016.12.014
CONFLICT OF INTEREST [12] A. Aznar, A. Gràcia-Condal, A. Planes, P. Lloveras, M.
Barrio, J.-L. Tamarit, W.X. Xiong, D.Y. Cong, C. Popescu, L.
The authors declare that they have no known Mañosa, Giant barocaloric effect in all-d-metal Heusler shape
memory alloys, Physical Review Materials 3(4) (2019)
competing financial interests or personal relationships 044406.
that could have appeared to influence the work https://doi.org/10.1103/PhysRevMaterials.3.044406
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Received on 27-07-2022 Accepted on 02-09-2022 Published on 19-10-2022

DOI: https://doi.org/10.31875/2410-2199.2022.09.06

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