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IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

Study on the Influence of Cu Content on Phase Transition

Characteristics of Fe75Ni(25-x)Cux Elastocaloric Refrigeration
Alloys

JiaXian Chen1a, YongJun Shi1b*, XianFa Li1c*, JunYuAn1d, and YaBin Yang2e
1
Mechanical and Electrical Engineering Institute, China University of Petroleum of
Huadong, Qingdao, Shandong Province, 266580, China
2
College of Computer and Artificial Intelligence, Henan Finance University,
Zhengzhou, Henan Province, 451470, China
a1
chenjiaxianupc @ 163. com, b1*Shiyj_upc @ 126. com, c1*lixianfa_oyjc @ 163.com,
d1
anjunyu2022 @ 163.com, e2yangyabin2022 @ 163.com.

Abstract: In this study, the mechanical alloying (AM) and powder metallurgy (PM) techniques
were adopted to synthesize the Fe75 Ni(25-x) Cux elastocaloric refrigeration alloys to research the
effect of Cu contents on phase transition characteristics and microstructure of Fe75Ni(25-x) Cux
elastocaloric refrigeration alloys. The conclusion was drawn that, with increasing Cu content,
the phase transition characteristics changed and presented different changing trends. It was
found that the phase enthalpy change value was 43.34J/g when the Cu content was 7at%,
which was about 1.26 times of Fe15Ni (wt%) alloy. In addition, the FeNiCu alloy was a
single-phase alloy with a crystal space group structure of Im-3m when the Cu content was
7at%, and the FeNiCu alloy was a two-phase alloy with crystal space group structures of
Im-3m and Fm-3m when the Cu content was more than 7at%. This study provided an
experimental basis for the theoretical investigation of the phase transition mechanism of
FeNiCu elastocaloric refrigeration alloys.

1. Introduction
Over the last few years, with the continuous discharge of greenhouse gases, the greenhouse effect has
attracted wide attention [1]. Therefore, with the introduction of new refrigeration concepts,
elastocaloric refrigeration technology has aroused wide concern from research and industrial
communities because of its high efficiency and environmental protection.
Changing the crystal structure of the elastocaloric refrigeration alloy from austenite and martensite
by exerting and removing the external stress or thermal field can make the realization of heat release
and absorption [2]. Among various elastocaloric refrigeration materials, the shape memory alloys, for
example,Ni-Mn-based [3], Ni-Ti-based [4], Cu-based [5], and Fe-based [6,7] alloys are commonly
considered to possess good properties and be widely studied.
At present, the research on elastocaloric refrigeration alloys has been conducted mainly on
following fields, including Ni-Ti-based elastocaloric refrigeration alloys [8], advanced manufacturing
process methods [9], elastocaloric refrigeration mechanisms [10], and elastocaloric refrigeration devices
[11]
. However, few explorations were reported on Fe-based elastocaloric refrigeration alloys. FeNiCu
alloy, which is a new kind of elastocaloric refrigeration alloy, possesses the strengths of economical
cost, convenient manufacturing techniques, and higher phase change enthalpy. Due to those

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IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

advantages, FeNiCu alloy has the latent capacity to take the place of traditional refrigeration materials.
Therefore, in this work, by using powder metallurgy technique, FeNiCu elastocaloric refrigeration
materials with different Cu contents were synthesized to research the effect of the content of Cu on the
phase transition characteristics of FeNiCu elastocaloric refrigeration alloys. Firstly, FeNiCu alloy
samples with initial Cu content of 7at%, 9at%, 11at%, and 13at% were synthesized by mechanical
alloying and powder metallurgy techniques, respectively. Then, the effect of the content of Cu on the
phase transition characteristics of FeNiCu elastocaloric refrigeration alloys was investigated by a
differential thermal scanner (DSC). Finally, the phase contents,microstructure, and crystal structure of
the FeNiCu elastocaloric refrigeration alloy were detected by Scanning electron microscope (SEM),
X-ray energy dispersive spectroscopy (EDS), and X'Pert-Pro ray diffractometer (XRD). This study
provided an experimental basis for the theoretical research on the phase transition mechanism of
FeNiCu elastocaloric refrigeration alloys.

2. Experimental process

2.1 Specimen preparation

The effect of Cu contents on phase transition characteristics of Fe75Ni(25-x) Cux elastocaloric
refrigeration alloys was researched through changing the content of the Cu element. Four groups of
FeNiCu samples were prepared, and the initial content of Cu in the four groups of samples was 7at%,
9at%, 11at%, and 13at%, respectively. A high-energy ball mill was used to adequately blend and make
the Fe, Ni, and Cu powder alloyed. Afterwards, at a ratio of ball to material of 10:1, ball-milling was
conducted at a velocity of 280 r/min for 480 minutes. After preparing four sets of FeNiCu alloy
powders with different proportions, the mixed powders were poured into the mold. And the powders
was statically pressed into a mold with a diameter of 15mm and a height of 6mm by press machine.
The pressure was regulated at 330-350MPa and held for 5min [12].

2.2 Sintering process

Through mechanical alloying and compression moulding, four specimen were prepared.Then the
specimens were placed in a vacuum sintering furnace. After heating to 1100°C and holding for 2 hours
in an argon-filled environment, the samples were cooled to 600°C for 2 hours to make the alloying
elements more evenly distributed. Meanwhile, the grains would regenerate into smaller grains to
improve their thermodynamic properties.

3. Characteristics testing

3.1. Phase transition characteristics testing

The FeNiCu alloy specimens were sliced into the suitable dimensions by applying wire cut electric
discharge machining technology. Afterwards the phase transition characteristics were tested by using
DSC at a scanning speed of 10°C/min and the range of temperature was 0°C to 480°C. Fig.1 and
Table1 showed the outcomes of the phase transition characteristics.

2
IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

(a) 4 Heating line (b) Heating line

3
3 Cooling line Cooling line
Martensite Austenite 2 Martensite Austenite

Heating Flow (mW)

Heating Flow (mW)

2
Cooling Cooling
1 37.14ºC
10.25ºC
1
43.53ºC
2.65J/g 16.64ºC
0 0 0.13J/g
438.20ºC
-1 -1 390.38ºC
-8.24J/g
-2 433.04ºC
391.43ºC -2 Martensite Austenite
-3 Martensite Austenite -40.69J/g Heating
Heating -3
-4
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Temperature (ºC) Temperature (ºC)
(c) 6 Heating line (d) Heating line
4
4 Martensite Austenite Cooling line Martensite Austenite Cooling line
Cooling Cooling

Heating Flow (mW)

Heating Flow (mW)

2 10.26ºC
2 8.98ºC 48.69ºC 32.04ºC

5.24J/g 1.63J/g

0 0

-2 -2
422.68ºC 437.45ºC
-4 409.98ºC 449.02ºC Martensite Austenite
Martensite Austenite -4
Heating -1.24J/g
Heating -2.16J/g

-6
-6
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
Temperature (ºC) Temperature (ºC)
Fig.1 Phase transition characteristics results. (a) Cu-7at%; (b) Cu-9at%; (c) Cu-11at%; (d) Cu-13at%.

Table 1. Phase transition characteristics

Cu (at%) As (℃) Af (℃) Ms (℃) Mf (℃) △HA (J/g) △HM (J/g)
7 391.43 433.04 37.14 10.25 -40.69 2.65
9 390.38 438.20 43.53 16.64 -8.24 0.13
11 409.98 449.02 48.69 8.98 -1.24 5.24
13 422.68 437.45 32.04 10.26 -2.16 1.63

3.2. Microstructure detections

The phase analysis of the phase composition, content, and crystal space group structure of the FeNiCu
elastocaloric refrigeration alloy was conducted by using the XRD. The detection parameters were
listed bolow: cobalt target, scanning range was 20°-110°, scanning speed was 1°/min. [12] The XRD
detection results were pictured in Fig.2. Fig.2 illustrated that the FeNiCu alloy with Cu content of
7at% had a BCC phase with a crystal space group structure of Im-3m. FeNiCu alloys with Cu contents
of 9at%, 11at%, and 13at% presented the crystal space group structures of Im-3m and Fm-3m,
respectively. The BCC phase content and FCC phase content were shown in Table 2. Table 2 indicated
that with increasing Cu content, the content of BCC phase (Im-3m) decreased, and the content of FCC
phase (Fm-3m) increased.

3
IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

(a) Obs. (b) Cu-9at% Obs.

Cu-7at%
Clac. Clac.
Diff. Diff.
Bragg_position Bragg_position

Intensity
Intensity

Im-3m PDF# 65-7753

Im-3m PDF# 65-7753
Fm-3m PDF# 65-5131

20 40 60 80 100 20 40 60 80 100
2 (deg.) 2 (deg.)
(c) (d) Obs.
Cu-11at% Obs. Cu-13at%
Clac. Clac.
Diff. Diff.
Bragg_position Bragg_position

Intensity
Intensity

Im-3m PDF# 65-7753

Fm-3m PDF# 65-5131 Im-3m PDF# 65-7753
Fm-3m PDF# 65-5131

20 40 60 80 100 20 40 60 80 100
2 (deg.) 2 (deg.)
Fig.2 XRD diffraction pattern of FeNiCu alloy. (a) Cu-7at%; (b) Cu-9at%; (c) Cu-11at%; (d)
Cu-13at%.

Table 2. The contents of BCC and FCC phases with Cu content of 7at%, 9at%, 11at%, and 13at%.
Cu(at%) BCC(Im-3m) % FCC(Fm-3m) %
7 100.00 0
9 94.11 5.89
11 91.10 8.90
13 87.45 12.55
SEM was used to characterize the microstructure of the samples. The FeNiCu alloy specimens were
sliced into the suitable size by applying wire cut electric discharge machining technology before
testing. Specimens were inlaid in white electric jade powder for microscopy. The silicon carbide
sandpaper was used to polish the inlaid specimens. And the grit size began at 400 and subsequently
decreasing it to 600, 800,1000, 1200,1500, 2000, and 3000. The 2.5 mm diamond paste was used to
furher polishing. A COXEM-30-plus desktop-scanning-electron-microscope was employed to seize
the microstructure images of the specimens. The SEM results were conducive to demonstrate the
results acquired from the X-Ray diffraction. The SEM images post-processing was carried out. The
microstructure images of the four sets of FeNiCu alloys were shown in Fig.3, Fig.4, Fig.5, and Fig.6 .
And the EDS was used to detecte the alloy elements[12]. This analysis provided help to verify whether
the content of each element in the alloy was consistent with the theoretical content. EDS test results
were shown in Table 3.

Fig.3 The microstructure image of the alloy with 7at% Cu content. (a) 1k times; (b) 10k times.

4
IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

Fig.4 The microstructure image of the alloy with 9at% Cu content. (a) 1k times; (b) 10k times.

Fig.5 The microstructure image of the alloy with 11at% Cu content. (a) 1k times; (b) 10k times.

Fig.6 The microstructure image of the alloy with 13at% Cu content. (a) 1k times; (b)10k times.

Table 3. EDS results of FeNiCu alloys with Cu content of 7at%, 9at%, 11at%, and 13at%.
Cu(at%) Area Fe Ni Cu O Ca Si Mn Mg C Al Na K
Area I 76.6 16.1 7.4 - - - - - - - - -
7
Area II 13.3 - - 45.9 14.7 14.7 2.8 1.9 6.7 - - -
Area I 75.4 15.4 9.2 - - - - - - - - -
9
Area II 13.1 - - 47.5 16.2 15.9 4.8 2.5 - - - -
Area I 75.7 14 11.3 - - - - - - - - -
11
Area II 11.5 - - 45.1 18.1 18 4.7 2.7 - - - -
Area I 75.4 11.4 13.2 - - - - - - - - -
13
Area II 9.1 - - 51.8 9.8 14.8 2.1 1.7 - 5.9 3.3 1.4

4. Result and discussion

4.1 Phase transition characteristics

The effects of the content of Cu on the transition temperature and enthalpy of FeNiCu elastocaloric
refrigeration alloy was shown in Fig.7 and Table 1. Fig.7 (a) indicated that As was kept between 390℃
and 430℃, which first showed a slowly declining and then a sharply increasing trend with the increase
of Cu content. When Cu content was 9at%, As reached the lowest value which was 390.38 ℃. As
shown in Fig.7(b), Af was kept between 430 ℃ and 450 ℃, which showed the first rising and then
dropping trend with the increase of Cu content. When Cu content was 11at%, Af reached the highest
value which was 449.02 ℃.
Fig.7 (c) illustrated that Ms was kept between 30℃ and 50℃, and showed a first increasing and
then decreasing trend with the increase of Cu content. When Cu content was 11at%, Ms reached the

5
IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

highest value which was 48.69℃. Mf was kept between 8℃ and -18℃ and showed the first rising,
then dropping, and finally rising trend with the increase of Cu content. When Cu content was 11at%,
Mf reached the lowest value which was 8.98℃ as shown in Fig.7(d).
The phase transition enthalpy was recognized as the key thermal parameter of elastocaloric
refrigeration alloy, which was the change value of enthalpy between the martensite transition and
austenite transition.Fig.7 (e) and Fig.7 (f) shown that, with increasing Cu content, the enthalpy value
△HA of the austenite transition process increased firstly and then decreased. It can be seen that the Cu
content had a great influence on △HA. When Cu content was 7at%, △HA reached the highest value
which was 40.69J/g, but the enthalpy value △HM of the martensite transition process was only 2.65
J/g. With the increase of Cu content, △HM showed the first dropping and then a rising trend. When
Cu content was 11at%, △HM reached the highest value which was 5.24J/g. Compared to the effect of
Cu content on the △HA, the influence of Cu content on the △HM was much smaller. Therefore, it can
be concluded that, when the Cu content was 7at%, the comprehensive phase transition characteristics
of FeNiCu elastocaloric refrigeration alloy reached the optimum. At this time, the phase change
enthalpy was 43.34J/g which was about 1.26times of the Fe15Ni(wt%) elastocaloric refrigeration alloy
(34.43 J/g) [7].
(a) (c) 55
(b)455 Ms
430 As Af
450 50
420 45
445

Ms (ºC)
As (ºC)

Af (ºC)

410 440 40

400 435 35

390 430 30

380 425 25
5 7 9 11 13 15 5 7 9 11 13 15 5 7 9 11 13 15
Cu (at%) Cu (at%) Cu (at%)

(d) 20 (f) 6 (e)

Mf HM HA
18 0

16 4
-10
HM (J/g)

HA (J/g)
Mf (ºC)

14
-20
12 2
10 -30
8 0
-40
6
5 7 9 11 13 15 5 7 9 11 13 15 5 7 9 11 13 15
Cu (at%) Cu (at%) Cu (at%)

Fig.7 Effect of Cu content on transition characteristics of FeNiCu alloy. (a) Effect of Cu content on As;
(b) Effect of Cu content on Af; (c) Effect of Cu content on Ms; (d) Effect of Cu content on Mf; (e)
Effect of Cu content on △HA; (f) Effect of Cu content on △HM;

4.2 Microstructure
According to the results of XRD and SEM, which were shown in Fig.2 to Fig.6. It can be seen that the
FeNiCu alloy with Cu content of 7at% had a BCC phase with a crystal space group structure of Im-3m.
Besides, FeNiCu alloys with Cu contents of 9at%, 11at%, and 13at% presented the crystal space group
structures of Im-3m and Fm-3m, respectively, which was different from the Fe14.6Ni(at%)
elastocaloric refrigeration alloy (IM-3m 229) [7]. Table 2 demonstrated that with increasing Cu content,
the content of the BCC phase (Im-3m) decreased, and the content of the FCC phase (Fm-3m)
increased. It can be concluded that with the increase of Cu content, FeNiCu elastocaloric refrigeration
alloy transformed from the BCC phase into the FCC phase. As a result, the phase transition
characteristics were changed.

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IFEMMT-2022 IOP Publishing
Journal of Physics: Conference Series 2459 (2023) 012013 doi:10.1088/1742-6596/2459/1/012013

5 Conclusion
Based on the above results and discussions, it can be concluded that the phase transition characteristics
changed with increasing Cu content and appeared different tendencies. And the phase change enthalpy
reached 43.34J/g when the Cu content was 7at%, which was about 1.26 times of Fe15Ni(wt%)
elastocaloric refrigeration alloy. Furthermore, the FeNiCu alloy with Cu content of 7at% showed an
IM-3m 229 crystal space group structure. With the increase of the Cu content, FeNiCu alloys
presented both IM-3m 229 and FM-3m 221 crystal space group structures with Cu contents of 9at%,
11at%, and 13at%, which was different from the Fe14.6Ni(at%) elastocaloric refrigeration alloy
(IM-3m 229). This study provided an experimental basis for the theoretical investigation of the phase
transition mechanism of FeNiCu elastocaloric refrigeration alloys. Further, the mechanism of the
influence of Cu content on FeNiCu elastocaloric refrigeration alloy needed to be investigated.

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