Eur. Phys. J.

Plus (2019) 134: 66

DOI 10.1140/epjp/i2019-12479-3
THE EUROPEAN
PHYSICAL JOURNAL PLUS
Regular Article

Influence of Ni addition and heat treatment on phase

transformation temperatures and microstructures of a ternary
CuAlCr alloy
F. Dagdelen1,a , M.A.K. Aldalawi1 , M. Kok1 , and I.N. Qader1,2
1
Firat University, Faculty of Science, Department of Physics, Elazig, Turkey
2
University of Raparin, College of Science, Department of Physics, Sulaimanyah, Iraq

Received: 26 October 2018 / Revised: 21 November 2018

Published online: 15 February 2019

c Società Italiana di Fisica / Springer-Verlag GmbH Germany, part of Springer Nature, 2019

Abstract. In this paper, Cu85 Al12 Cr3 and Cu83 Al12 Cr3 Ni2 (wt. %) high temperature shape memory alloys
(HTSMA) were fabricated from highly pure powder elements by using an arc melter. After production,
some pieces of alloys were subjected to heat treatment at 1073 K for one hour. Then, Differential Scanning
Calorimeter (DSC), Optical Microscopy (OM), X-Ray Diffraction (XRD), Vickers microhardness, and
Scanning Electron Microscopy (SEM) analyses were carried out to investigate thermodynamic parameters,
microstructure, crystal structure, mechanic properties, and to determine precipitation types in non-heat-
treated and heat-treated alloys, respectively. According to the results of DSC measurements, both alloys
showed a high temperature shape memory effect; also, the phase transformation temperatures of the alloys
were affected by the heat treatment. The analysis of XRD patterns showed two different predominant
microstructures in both alloys, i.e. γ1 and β1 phases. Moreover, microstructural results showed the influence
of Ni additive in decreasing the size of the grains and the number of the precipitates. In addition, micro-
hardness, as a mechanic property, decreased through adding Ni to the CuAlCr alloy.

1 Introduction
Cu-based shape memory alloys (SMAs) have been widely utilized in numerous practical applications due to the unique
properties of pseudoelasticity, damping capability and shape memory effect [1–3]. CuAl and CuZn are two primary Cu-
based SMAs exploited in the field of the β-phase. Certainly, for high temperature applications, CuAl-based SMAs are
widely employed [4–6]. It has been reported that heat treatment of Cu-based SMAs makes a significant change in phase
transformation characteristics. Since these types of SMAs are economically moderate related to the most prevalent
NiTi-based SMAs, they are presented as potential alternatives. Nonetheless, Cu-based SMAs are still at developing
stage and only a few commercial applications are available due to their poor mechanical properties and low thermal
stability [4,7,8]. In recent years, there has been an important development in their mechanic and thermodynamic
properties by adding new elements [9–12] or performing heat treatment [12,13]. In this way, Cu-based SMAs can serve
as both high temperature shape memory alloys (HTSMAs) and durable materials [14].
In this paper, a ternary Cu85 Al12 Cr3 and a quaternary Cu83 Al12 Cr3 Ni2 shape memory alloys were fabricated from
highly pure powder, and then all alloys were subjected to heat treatment at 1073 K for one hour. Mechanical, thermal
and microstructural properties of the main alloys and heat-treated alloys were investigated by Differential Scanning
Calorimeter (DSC), Optical Microscopy (OM), X-Ray Diffraction (XRD), Vickers microhardness measurement, and
Scanning Electron Microscopy (SEM).

2 Experimental procedure
Firstly, Cu, Al, Cr, and Ni metal powders with 99.9% purity were prepared by weight percent (wt. %) in the desired
compositions. Table 1 lists the composition rates of each alloy. The powders were mixed with an 8–10 mm diameter
ceramic ball in a mechanical mixer. After that, mixed metal powders were shaped as 13 mm diameter pellets (discs)
a
e-mail: fethidagdelen@gmail.com (corresponding author)
Page 2 of 6 Eur. Phys. J. Plus (2019) 134: 66

Table 1. The weight and atomic percentages of fabricated samples.

Cu Al Cr Ni
CuAlCr wt % 85.00 12.00 3.00 –
at.% 73.80 24.44 3.16 –
CuAlCr wt % 83.00 12.00 3.00 2.00
at.% 71.00 23.36 3.11 1.86

CuAlCr
200 CuAlCrNi
CuAlCr (800oC)
150 CuAlCrNi (800 oC)

100
DSC ( μW/mg)

50

-50

-100

-150

-200
0 50 100 150 200 250 300 350 400 450 500
o
Temperature ( C)
Fig. 1. Phase transformation curves of samples non-heat-treated and heat-treated CuAlCr and CuAlCrNi HTSMAs.
Table 2. Transformation temperatures and enthalpy results of samples.
Sample As Af To Ms Mf ΔH Hardness
(K) (K) (K) (K) (K) (J/g) (HV0.5 )
CuAlCr 575.1 672.4 545.9 516.7 460.9 3.35 289.0
CuAlCrNi 529.3 572.1 505.9 482.5 421.2 2.80 263.0
Heat-treated CuAlCr 574.8 658.2 587.1 599.4 488.5 6.51 261.2
Heat-treated CuAlCrNi 487.1 553.3 491.8 496.5 420.8 1.92 229.4

under a pressure of 10 MPa. Next, pellets were melted in an arc-melting system under argon atmosphere to avoid
oxidation. The melting process was repeated several times to homogenize both ternary and quaternary alloys. Then
they were kept in a furnace at 1200 K for 12 hours in air atmosphere; afterwards, alloys were immediately cooled down
with salt-iced water to obtain an ordered metastable β-phase. Also, some pieces of the CuAlCr and CuAlCrNi alloys
were subjected to heat treatment at 1073 K for an hour. After that, to perform DSC measurement, some light pieces
have been prepared from ingots of approximately 50 mg. Austenite and martensite phase transformation temperatures
were determined by means of Perkin Elmer Sapphire DSC from 273 to 773 K at a heating rate of 20 K/min in a nitrogen
atmosphere [15–18]. Also, to observe microstructures on the surface of each specimen, adequate plat-like samples were
cut and after polishing by using a chemical solution (10 ml HCl+25 ml FeCl3 +48 ml CH3 OH) their surfaces were etched.
Moreover, the crystal structure of the alloys was determined by XRD measurement (Rigaku RadB-DMAX II with
Kα = 1.543 nm) at room temperature for 2θ values from 20◦ to 80◦ . In addition, Vickers hardness test, set with 0.5 kg
for 10 s, was performed by Emco Test DuraScan to measure the microhardness of these alloys. Finally, microstructural
and elemental analysis was accomplished by SEM-EDX measurement (EVO 40XVP) at room temperature.

3 Results and discussion

3.1 Differential scanning calorimetry

The DSC curves, represented in fig. 1, correspond to the forward and the reverse martensitic transformation of ternary
CuAlCr and quaternary CuAlCrNi alloys for both as-received and heat-treated alloys. Also, their transformation tem-
peratures were found and listed in table 2. Both alloys can be classified as types of HTSMA, since the CuAlCr alloy has
Eur. Phys. J. Plus (2019) 134: 66 Page 3 of 6

Fig. 2. XRD pattern of non-heat-treated and heat-treated CuAlCr and CuAlCrNi HTSMAs.

phase transformation temperatures as As = 575.3 K, Af = 672.6 K, Ms = 516.9 K and Mf = 461.0 K, while the same
quantities for CuAlCrNi alloy as As = 529.3 K, Af = 572.1 K, Ms = 482.5 K. The results show that the CuAlCrNi alloy
has notably lower phase transformation temperature values. In a similar study, Zare and Ketabchi [19] added chromium
as a fourth element, in the CuAlNi alloy; they found that the transformation temperature of the alloy decreases with the
addition of chromium. Another important result is that the heat treatment led to reducing the transformation tempera-
tures in both alloys. In a previous study [2], the effect of the heat treatment on the quaternary CuAlNiHf shape memory
alloy was studied and it was found that heat treatment at 1173 K leads to the most stable phase compared to other
samples. Moreover, the change of specific enthalpy, from martensite phase to austenite phase transformation is 3.35 J/g
and 2.80 J/g for the ternary CuAlCr and the quaternary CuAlCrNi alloys, respectively. Thereby, to transform from
martensite phase to austenite phase, the CuAlCr alloy needs approximately 0.55 J/g more than the CuAlCrNi alloy.

3.2 X-ray diffraction

X-ray measurements for the range of 30◦ –80◦ were acquired at room temperature. Figure 2 illustrates some peaks with
different intensity for both CuAlCr and CuAlCrNi shape memory alloys, which were indexed by using the literature
data [1,12,20,21]. It can be observed that the γ1 and β1 phases are the two predominant phases in both CuAlCr
and CuAlCrNi alloys. While both these phases are martensite, they have substantial differences in their morphology.
Page 4 of 6 Eur. Phys. J. Plus (2019) 134: 66

Fig. 3. Optical and SEM microstructures of non-heat-treated CuAlCr and CuAlCrNi. (a) and (c): optical microstructure; (b)
and (d): SEM images.

The γ1 phase is a thin-type martensite, the β1 phase is a thick-type martensite phase. From XRD pattern, different
planes indicated for each phases, for instance (202) and (0018), belong to the γ1 phase, whereas (128), (2010), (2128)
and (0412) are the defined planes of the β1 phase [15]. However, in the CuAlCr HTSMA, the γ1 phase is higher than
the β1 phase, which is sharp in the CuAlCrNi alloy.
X-ray diffractograms of alloys, which exposed to 800 ◦ C for an hour, is shown in fig. 2(b). It is clear that heat
treatment at 800 ◦ C did not change martensite phases in the CuAlCr and CuAlCrNi alloys. There are thin and thick
martensite phases in alloys. The XRD peak intensity of the heat-treated alloys is sharper compared to that of the
other alloys. When the alloys are exposed to heat treatment at 800 ◦ C for an hour, peaks intensities increased and a
distortion of X-ray values disappeared, which caused peaks to be clearer.

3.3 Microstructure and hardness

SEM and optical micrographs of CuAlCr and CuAlCrNi SMAs are given in figs. 3(a)–(d). Both alloys have a large
number of grains in their structures and they consist of a significant amount of martensite plates. In addition, there
is much precipitations spread in the matrix of both alloys, which consist of approximately 10 μm and 4 μm for the
CuAlCr and CuAlCrNi alloys, respectively. The decrease in the size of precipitations and the increase in their numbers
could be due to the addition of Ni additive. Furthermore, the grain sizes of the CuAlCr alloy are approximately 200 μm,
whilst Ni addition makes the size of grains decrease to around 120 μm. Thus this improvement in the grain size could
cause a decrease in the brittleness of the alloy. The same improvement has been reported by some researchers via
adding an additional alloying element to Cu-based SMAs or performing heat treatment [12,22–26]. Saud et al. [12]
used silver to reduce micro cracks and internal stress of the Cu-Al-Ni alloy due to the high interaction of Ag with the
base-alloying element. On the other hand, Sutou and colleagues [23] found the ageing of the Cu-Al-Mn-Ni-B shape
memory alloy to increase tensile strength, while pseudoelasticity was not affected.
The microstructure of the CuAlCr and CuAlCrNi alloys, which were exposed to a 800 ◦ C temperature, is illustrated
in figs. 4(a)–(d). Optical microscopy shows that there are lot of grains and precipitates in the structure of both alloys.
According to EDX analyses, these grains have martensite plates and these participates are Cr participates. The SEM
images show the grain borders, obviously, and they exhibit martensite plates as well.
Eur. Phys. J. Plus (2019) 134: 66 Page 5 of 6

Fig. 4. Optical and scanning electron microscopy results of heat-treated CuAlCr and CuAlCrNi at 800 ◦ C. Here, (a) and (b)
are optical microstructure images, whereas (c) and (d) are SEM images.

Vickers hardness measurements for both alloys were performed, and the results are listed in table 2. The results show
that addition of Ni to the CuAlCr alloy dropped microhardness value, which may due to increasing the precipitates in
the structure, and/or via the effect of grain size reduction. The hardness value of alloys, exposed to 800 ◦ C for an hour,
can be seen in table 2. The hardness value of the CuAlCr alloy decreased from 289 to 261.2 HV due to heat treatment.
The same reduction was found in the CuAlCrNi alloy from 263 to 229.4 HV. Qader et al. [2] reported that the α and
β1 phases increase due to heat treatment of the CuAlNiHf alloy and, thus, the value of micro-hardness decreases.

4 Conclusions

The influence of Ni as an additive to CuAlCr SMA was studied, and thermal, mechanical and microstructural properties
of the alloys were investigated. Thus, from the analysis of the results, one can conclude that:

– Both Ni addition to the CuAlCr alloy and heat treatment at 800 ◦ C made a remarkable reduction in the transfor-
mation temperatures of alloys.
– The X-ray pattern of alloys revealed various martensite phases such as (202) and (0018) planes indicated the γ1
phase; besides (128), (2010), (2128), and (0412) planes represented β1 phase. Moreover, heat treatment made X-ray
peaks of alloys more clear.
– Micro-optical and SEM images showed that Ni additive reduced grain sizes and decreased precipitation.
– Ni addition and heat treatment cause a quantitative decrease in Vickers micro-hardness.

This work has been supported by the Management Unit of Scientific Research Projects of Firat University (FUBAP) (Project
Number: FF.13.08). It has been prepared from M.A.K. Aldalawi Master’s Thesis.
Page 6 of 6 Eur. Phys. J. Plus (2019) 134: 66

Publisher’s Note The EPJ Publishers remain neutral with regard to jurisdictional claims in published maps and institutional
affiliations.

References
1. S.N. Saud et al., Metall. Mater. Trans. A 47, 5242 (2016).
2. I.N. Qader, M. Kök, F. Dağdelen, Physica B 553, 1 (2018).
3. K. Otsuka, C.M. Wayman, Shape Memory Materials (Cambridge University Press, 1999).
4. F. Dagdelen et al., Mater. Lett. 57, 1079 (2003).
5. Y. Aydoğdu et al., J. Phys.: Conf. Ser. 667, 012010 (2016).
6. R. Dasgupta et al., J. Mater. Res. Technol. 3, 264 (2014).
7. G. Firstov, J. Van Humbeeck, Y.N. Koval, J. Intell. Mater. Syst. Struct. 17, 1041 (2006).
8. D. Stoeckel, Mater. Design 11, 302 (1990).
9. S.N. Saud et al., J. Therm. Anal. Calorim. 118, 111 (2014).
10. S. Saud et al., Trans. Nonferr. Metals Soc. China 25, 1158 (2015).
11. W.Y. Ci et al., J. Mech. Eng. Sci. 11, 2770 (2017).
12. S.N. Saud et al., J. Alloys Compd. 612, 471 (2014).
13. S.N. Saud et al., J. Therm. Anal. Calorim. 119, 1273 (2015).
14. S. Vajpai, R. Dube, S. Sangal, Mater. Sci. Eng. A 570, 32 (2013).
15. M.A.K. Al-Dalawi, Fabrication of Cu Based HTSMAs and Investigation of Their Physical Properties, in Physics (Firat
University, 2017).
16. F. Dağdelen et al., Eur. Phys. J. Plus 131, 196 (2016).
17. S. Buytoz et al., J. Therm. Anal. Calorim. 117, 1277 (2014).
18. I. Somunkiran, S. Buytoz, F. Dagdelen, J. Alloys Compd. 777, 302 (2019).
19. M. Zare, M. Ketabchi, J. Therm. Anal. Calorim. 127, 2113 (2017).
20. A. Pandey et al., Metall. Mater. Trans. B 47, 2205 (2016).
21. C. Wang et al., Smart Mater. Struct. 23, 025018 (2013).
22. Ş.N. Balo, N. Sel, Thermochim. Acta 536, 1 (2012).
23. Y. Sutou et al., Acta Mater. 57, 5759 (2009).
24. N. Suresh, U. Ramamurty, Mater. Sci. Eng. A 454, 492 (2007).
25. U. Sari et al., Int. J. Miner., Metall., Mater. 18, 430 (2011).
26. N. Suresh, U. Ramamurty, J. Alloys Compd. 449, 113 (2008).