Physica B 696 (2025) 416611

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Physica B: Condensed Matter

journal homepage: www.elsevier.com/locate/physb

Excellent mechanical properties and giant room-temperature elastocaloric

effect in spark plasma sintered Ni-Co-Mn-Ti shape memory alloy
Yanze Wu a,1 , Ziqi Guan b,**,1, Hongyuan Tang a , Zhenzhuang Li a,b,* , Zongbin Li c,***,
Yanxu Wang b, Xing Lu a , Liang Zuo c
a
School of Material Science and Engineering, Dalian Jiaotong University, Dalian, 116028, China
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
c
Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), School of Material Science and Engineering, Northeastern University, Shenyang,
110819, China

A R T I C L E I N F O A B S T R A C T

Keywords: All-d-metal Heusler-type Ni-Mn-Ti alloys have emerged as a research focus in the field of elastocaloric refrig­
Ni-Mn-Ti alloys eration due to their remarkable elastocaloric effect. However, the mechanical properties of these materials
Elastocaloric effect present a challenge for their engineering applications. In this work, Ni37Co13Mn33.5Ti16.5 alloys with varying
Spark plasma sintering
particle sizes were successfully prepared under different conditions using spark plasma sintering. The influence
Mechanical properties
of particle size on the microstructure, mechanical properties and the elastocaloric effect were systematically
explored. The results indicate that smaller particle sizes can significantly enhance mechanical properties during
the SPS process, primarily due to grain refinement and the presence of Ti-rich second phases within the grains.
Notably, compressive strength and fracture strain reached as high as 2225 MPa and 33 %, respectively, marking
an increase of 145.9 % and 312.5 % over the as-cast alloy. Additionally, an unprecedently adiabatic temperature
variation of 31.2 K was obtained upon loading in the sintered Ni-(Co)-Mn-Ti shape memory alloys.

1. Introduction [13], Heusler-type NiMn-based [14], and all-d-metal Heusler-type

Ni-(Co)-Mn-Ti alloys [9,15–17]. The all-d-metal Heusler-type Ni-Mn-Ti
The field of solid-state refrigeration has garnered significant interest alloys have shown substantial potential for elastocaloric cooling,
due to its higher efficiency and environmental benefits, positioning it as owing to their impressive elastocaloric properties associated with
a promising alternative to traditional vapor-compression refrigeration simultaneous large unit cell volume change (ΔV/ΔV0) and trans­
technologies [1,2]. Among various non-vapor-compression methods, formation entropy change (ΔStr) during the martensitic transformation
such as magnetocaloric [3], barocaloric [4], electrocaloric [5], and [9]. For example, a giant ΔTad value of 31.5 K was obtained in a
elastocaloric effects (eCE) [6] induced by magnetic, hydrostatic, electric (Ni50Mn31.5Ti18.5)99.8B0.2 polycrystalline alloy, which is attributed to a
and uniaxial stress fields, respectively, the latter is celebrated for its low large ΔV/ΔV0 of 1.89 % and an enormous ΔStr of 76 J kg− 1 K− 1 [9]. Such
device cost, high performance efficiency, and versatility across different findings underscore the importance of developing materials with high
climatic conditions, making it a particularly attractive option for ΔStr for efficient elastocaloric cooling. In addition, robust mechanical
solid-state cooling applications [6–9]. The eCE is usually characterized property is the fundamental condition for obtaining the ΔTad of the
by adiabatic temperature variation (ΔTad) or the isothermal entropy elastocaloric effect. Developing columnar-grained structures with a
change (ΔSσ), originating from the release or the absorption of latent strong textured microstructure through directional solidification has
heat on the application or removal of the uniaxial field [10]. proven effective. For instance, the directionally solidified Ni45.7C­
To date, eCE has been extensively studied in various shape memory o4.2Mn37.3Sb12.8 alloy exhibited a compressive strength of ~740 MPa
alloys including NiTi-based [11], CuMnAl-based [12], NiFeGa-based and a ΔStr of − 31.6 J kg− 1 K− 1, contributing to a notable ΔTad of 9.4 K

* Corresponding author. School of Material Science and Engineering, Dalian Jiaotong University, Dalian, 116028, China.
** Corresponding author.
*** Corresponding author.
E-mail addresses: [email protected] (Z. Guan), [email protected] (Z. Li), [email protected] (Z. Li).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.physb.2024.416611
Received 26 August 2024; Received in revised form 1 October 2024; Accepted 7 October 2024
Available online 9 October 2024
0921-4526/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
Y. Wu et al. Physica B: Condensed Matter 696 (2025) 416611

upon loading [18]. Although directional solidification and single crystal conventional arc melting with high-purity Ni (99.97 wt%), Co (99.99 wt
methods can improve the mechanical properties of shape memory al­ %), Mn (99.9 wt%) and Ti (99.99 wt%), annealed at 1223 K for 48 h, and
loys, these preparation methods are complex and time-consuming, then quenched in water. The obtained cast samples were mechanically
limiting the development of practical solid-state refrigeration applica­ milled to produce the alloy powder, which was then screened through a
tions in the future. national standard sieve into 0–48 μm, 48–74 μm, and 74–150 μm sizes,
The spark plasma sintering (SPS) technique, which facilitates the and then annealed for 6 h at 873 K for subsequent sintering. Sintering
rapid sintering of metal powders, has also demonstrated its efficacy in was carried out under 8 Pa vacuum and 50 MPa stress at a sintering
producing dense shape memory alloys with superior mechanical prop­ temperature of 1223 K. The SPS time for the samples with varying
erties [19,20]. It is reported that the compressive strength and fracture particle sizes of 48–74 μm and 74–150 μm was 20 min. The holding time
strain of the sintered Ni50Mn34.7In15.3 alloy up to 1800 MPa and 19.3 % for the four samples with varying particle sizes of 0–48 μm were 15 min,
were achieved, respectively, significantly surpassing those of the arc 20 min, 25 min, and 30 min, respectively. The sintered samples were
melted alloy [21]. It is well-known that the microstructure of shape annealed at 1223 K for 24 h and quenched in water. The martensitic
memory alloy is strongly dependent on the particle size and SPS con­ transformation temperatures of each alloy were tested using a Differ­
ditions, which significantly influence the compressive strength. How­ ential Scanning Calorimetry Analyzer (DSC: TA-Q100) with a ramp-up
ever, the effect of microstructure on the mechanical properties and eCE and ramp-down rate of 10 K min− 1. Mechanical properties were tested
of sintered all-d-metal Heusler-type Ni-(Co)-Mn-Ti alloys has not been on a universal mechanical testing machine equipped with a heating
revealed, despite its extreme importance. oven. The values of ΔTad induced by external stress were monitored at Af
This study focuses on the mechanical properties and eCE of SPS + 15 K by the means of a thermocouple clamped in the center of the
Ni37Co13Mn33.5Ti16.5 alloys with varying particle sizes. It was demon­ sample surface. The XRD measurements were carried out at 200 K and
strated that reducing particle size led to grain refinement and a Ti-rich 320 K by Multifunctional X-ray diffractometer. Prior to each measure­
second phase distribution within the grains, both of which contributed ment, the sample was firstly cooled/heated to the test temperature. Then
to increased compressive strength. Notably, a large compressive a rate of 2◦ /min within the scanning range of 30◦ –90◦ was measured.
strength of 2225 MPa and a fracture strain of 33 % were achieved in the The samples for microstructure determination were polished by a PG-1
sintered alloy. Moreover, a remarkable ΔTad of 31.2 K was recorded at automatic electrolytic polishing machine with 20 % methanol nitrate, at
room temperature upon loading, surpassing that of other sintered shape 12 V and 25 s. The microstructure of the alloys was observed by a JEOL
memory alloys. This investigation highlights the critical importance of JSM-7001F scanning electron microscope (SEM), and the composition
microstructural control through SPS for enhancing the functional was calibrated using energy-dispersive spectroscopy (EDS), with results
properties of elastocaloric materials. averaged over five measurements.

2. Experiments 3. Result and discussion

The cast Ni37Co13Mn33.5Ti16.5 alloy was first prepared by Fig. 1(a) illustrates the DSC curves of Ni37Co13Mn33.5Ti16.5 alloys

Fig. 1. (a) DSC plots of samples with varying particle sizes of the alloy and the arc-melted. (b) Entropy changes and thermal hysteresis of samples with varying
particle sizes and the arc-melted. (c) DSC plots of samples with different SPS time. (b) Entropy changes and thermal hysteresis of samples with different SPS times.

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Y. Wu et al. Physica B: Condensed Matter 696 (2025) 416611

with varying particle sizes. The data indicates that the martensitic times exhibit minimal variation. Fig. 1(d) presents the ΔThys and ΔStr of
transformation temperature increased gradually with decreasing pow­ the samples with varying particle sizes, and it also shows that the dif­
der particle size. This is because smaller grain sizes increase the incon­ ference is small.
sistency of the martensitic transformation, requiring more energy and Because triggering the eCE by stress-induced martensitic trans­
resulting in a higher martensitic transformation temperature [16]. The formation requires that the material be subjected to a considerable
samples with powder particle sizes ranging from 0 μm to 48 μm exhibit amount of stress, it is very important to obtain good mechanical prop­
transformation temperatures (Ms, Mf, As, and Af) closest to room tem­ erties. Fig. 2(a) displays the stress-strain curves of the samples with
perature. These transformation temperatures, determined by the different powder particle sizes and arc-melted sample. The mechanical
tangent method, were 265.9 K, 250.5 K, 267.5 K, and 282.5 K, properties of the SPS samples were found to be significantly enhanced
respectively. compared to those of the arc-melted sample (i.e., 904 MPa). The sample
The thermal hysteresis (ΔThys) of the martensitic transformation was with powder particle sizes of 0–48 μm exhibited the best mechanical
calculated from the martensitic transformation temperatures ( (Ms, Mf, As, properties, with a maximum strain at fracture of 33 % and a maximum
and Af) obtained from DSC measurements using ΔThys = As+ Af − Ms − compressive strength of 2225 MPa. Fig. 2(b) presents the strength of the
)
Mf /2. The value of ΔStr for the inverse martensitic transformation was samples with varying SPS times, and the difference is also small.
calculated by the formula ΔStr = ΔHtr /T0 , where ΔHtr is the enthalpy The comparison of mechanical properties between the present alloy
change of the transformation as determined by the DSC measurements and some other typical shape memory alloys is shown in Fig. 2(c), where
and T0 is the average transformation temperature estimated by T0 = DS represents directional solidification, P represents polycrystalline, and
( )
As + Af /2. Fig. 1(b) shows the ΔThys and ΔStr of the samples with S represents spark plasma sintering. The results indicate that the ulti­
varying particle sizes It can be seen that the samples of 0–48 μm sizes mate compression strength of the present alloy (i.e., 2225 MPa) is
have the lowest ΔThys (i.e., 16.8 K) and the largest ΔStr (i.e., 37.82 J significantly higher than that of previously reported shape memory al­
kg− 1 K− 1), which shows optimal comprehensive performance. loys [17,20–28]. The excellent mechanical properties of the sintered
Fig. 1(c) shows the DSC curves of different SPS times for samples Ni37Co13Mn33.5Ti16.5 alloys are of great importance for the subsequent
with powder particle sizes of 0–48 μm. It indicates that the martensitic measurements of elastocaloric effects.
transformation temperatures of the samples subjected to different SPS Fig. 3(a) shows the ΔTad values of samples loaded under the rates of
0.028 s− 1 and 0.28 s− 1 for different powder particle sizes. The results

Fig. 2. (a) Compressive stress-strain curves of samples with varying particle sizes and arc-melted at room temperature with a loading and unloading rate of 0.0014
s− 1. (b) Compressive stress-strain curves of SPS time samples with varying particle sizes at room temperature with a loading and unloading rate of 0.0014 s− 1. (c)
Comparison on the mechanical properties between the present alloy and some other typical shape memory alloys reported in the literatures.

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Y. Wu et al. Physica B: Condensed Matter 696 (2025) 416611

Fig. 3. (a) Thermal adiabatic temperature change of samples with varying particle sizes, measured at Af + 15 K (Af: austenitic transformation finish temperature). (b)
Adiabatic temperature change of samples with different SPS times, measured at temperatures higher than Af + 15 K. (c) Time dependence of adiabatic temperature
change on loading with various compressive strains. (d) Cyclic DSC curves of SPS sample.

illustrate that the ΔTad values of the samples with powder particle sizes measurements were carried out from 223 K to 313 K for sintered
of 74–150 μm and 48–74 μm are not significantly different. However, Ni37Co13Mn33.5Ti16.5 alloys with particle size of 0–48 μm, as shown in
when the powder particle size decreases to 0–48 μm, the ΔTad value Fig. 3(d). The results show that the transformation temperature only
increases significantly (i.e., 29 K at a rate of 0.28 s− 1), demonstrating migrates 1 K after 50 heating/cooling thermal cycles, which demon­
that smaller powder particle size enhances the eCE of sintered Ni-(Co)- strates that the SPS Ni37Co13Mn33.5Ti16.5 alloys exist excellent cyclic
Mn-Ti shape memory alloys. For subsequent measurements, sintered functionality.
alloys with powder particle size of 0–48 μm were employed. Fig. 4 displays the XRD patterns measured at 320 K and 200 K for SPS
Fig. 3(b) shows SPS time dependence of ΔTad on loading with a
maximum compressive strain of 12 %. The insets in Fig. 3(a) and (b)
show the stress-strain curves corresponding to the ΔTad measurements.
It can be seen that the ΔTad values for different SPS times for powder
particle size of 0–48 μm are similar, showing significant enhancement
compared to the results presented in Fig. 3(a) (powder particle sizes of
74–150 μm and 48–74 μm). Notably, a maximum ΔTad as high as 31.2 K
was achieved at the rate of 0.28 s− 1 with SPS time of 25 min. The
enhanced ΔTad values are attributed to the higher ΔStr of sintered
Ni37Co13Mn33.5Ti16.5 alloys with particle size of 0–48 μm compared to
those with larger particle sizes (as demonstrated in Fig. 1(b) and (d)).
Fig. 3(c) shows the time dependence of ΔTad values on loading for
sintered Ni37Co13Mn33.5Ti16.5 alloys with particle size of 0–48 μm under
various compressive strains with the strain rate of 0.28 s− 1. It can be
seen that with an increase in the compressive strain from 4 % to 12 %,
the maximum values of ΔTad increase gradually from 5.3 K to 31.2 K
during loading. This is mainly because the volume fraction of the stress-
induced transformation from austenitic phase to martensitic phase
gradually increases with the increase of the maximum compressive
strains [9]. In order to determine the cyclic stability, the cycle DSC Fig. 4. XRD patterns measured at 320 K and 200 K for SPS sample.

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Y. Wu et al. Physica B: Condensed Matter 696 (2025) 416611

sample with powder particle sizes of 0–48 μm. The austenite phase has a phase and the martensite phase. Second phase particles can increase the
cubic L21 structure with the lattice parameter aA = 5.916 Å. At the test critical stress required for phase transformation, thereby enhancing the
temperature of 200 K, it is evidenced that the martensite phase is six- transformation stress of the material. This means that under the same
layered modulated (6 M), with the lattice constants of aM = 4.385 Å, external stress, sintered Ni37Co13Mn33.5Ti16.5 alloys with the second
bM = 5.474 Å, cM = 12.870 Å and β = 96.5◦ . It is indicated that a large phase at the grain boundaries are less likely to undergo phase trans­
unit cell volume change ΔV/V0 of 1.2 % can be achieved from the formation. Based on this, the SPS process can enhance the grain
austenite phase to martensite phase, which should be attributed to the boundary strength, improving the mechanical properties of the sample
large ΔStr and is the main reason for the significant elastocaloric effect. without altering the original properties of the material [29–31]. In
Moreover, very weak diffraction peaks can be observed at the 2θ of addition, the second phase further improves the mechanical properties
44.6◦ , suggesting the existence of second phase. of the material.
Fig. 5 shows the SEM pictures of different samples at room temper­ A comparison between the elastocaloric properties and ultimate
ature. It can be observed that the grain size decreases with the decrease compressive properties of the present alloy and some other typical
of the powder particle size, as shown from Fig. 5(a)–5(c). In addition, the caloric materials is shown in Fig. 6, where DS represents directional
SPS time does not change the grain size if the powder particle size is solidification, P represents polycrystalline, and SC represents single
determined, as shown from Fig. 5(c)–5(f). According to the Hall-Petch crystals. It is noted that although the ΔTad of sintered
effect, grain boundaries are the obstacles to dislocation movement,
under the action of an external force. To induce shear deformation in
neighboring grains, it is necessary to generate grain boundaries under
conditions of high stress concentration. The refinement of grains can be
achieved by the formation of additional grain boundaries. However, if
the structure of the grain boundaries remains unchanged, it is necessary
to apply a greater external force in order to produce dislocation plug­
ging, thereby improving the strength of the material. The smaller the
particle size of the SPS powder, the smaller the grain size of the SPS
samples, and the higher the strength of the samples. Therefore, samples
with a particle size of 0–48 μm have the highest compressive strength, as
shown in Fig. 2(a).
Grain boundary brittleness is commonly observed in shape memory
alloys. Therefore, enhancing the grain boundary strength while main­
taining functionality is crucial for functional materials. Fig. 5(c) shows
that the SPS sample precipitates the Ti-rich second phase within the
grains and at the grain boundaries, which is consistent with the XRD test
results, as displayed in Fig. 4. In addition, the composition of the grains
is determined to be Ni36.8Co13.1Mn33.4Ti16.7, which is close to the
nominal composition. On one hand, the second phase located at grain
boundaries can prevent grain growth and inhibit grain boundary sliding,
thereby providing grain boundary strengthening and enhancing the
Fig. 6. Comparison on the elastocaloric properties and compressive strength
material’s strength. On the other hand, the presence of the second phase
between the present alloy and some other typical elastocaloric materials re­
can influence the phase transformation behavior between the austenite
ported in the literatures.

Fig. 5. (a), (b), (c) are the scanning images of the samples with powder particle sizes of 74 μm–150 μm, 48 μm–74 μm, 0 μm–48 μm, respectively, and Fig. 5(c), (d),
(e), (f) are the SEM images of the samples with powder particle sizes of 48 μm–74 μm and SPS times of 15, 20, 25, and 30 min, respectively.

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Y. Wu et al. Physica B: Condensed Matter 696 (2025) 416611

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