Thermochimica Acta 536 (2012) 15

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Effects of thermal aging on transformation temperatures and some physical

parameters of Cu13.5 wt.%Al4 wt.%Ni shape memory alloy
S. Nevin Balo a, , Neslihan Sel b
a
b

Firat University, Science Faculty, Department of Physics, 23169 Elazig, Turkey

Eren University, Science and Ards Faculty, Department of Physics, Bitlis, Turkey

a r t i c l e

i n f o

Article history:
Received 10 October 2011
Received in revised form 1 February 2012
Accepted 3 February 2012
Available online 22 February 2012
Keywords:
Shape memory
Gibbs free energy
Elastic strain energy
Vickers hardness

a b s t r a c t
The effects of thermal aging at a constant temperature above Af (austenite phase nish temperature) on
the martensitic transformation of the CuAlNi shape memory alloy were investigated. The evolution of
the transformation temperatures was studied by differential scanning calorimetry (DSC). It was found
that the thermal aging at a constant temperature above Af has a complex effect on the transformation
parameters of the CuAlNi shape memory alloy. The Ms , Mf , As , and Af transformation temperatures were
shifted by the thermal annealing. The thermodynamic parameters such as Gibbs free energy and the
elastic strain energy of the alloy experienced a decreasing tendency with increasing the aging time. The
structural properties of aged alloy samples were studied by X-ray diffraction measurements at room
temperature. It was found that the phase transformation parameters of the alloy are controlled by the
crystallite size effect.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Cu-based shape memory alloys (SMAs) have been paid more
attention in past few years owing to their low price, easy fabrication
and excellent conductivity of heat and electricity. Shape memory
alloys exhibit the remarkable thermomechanical properties like
pseudoelasticity (PE), shape memory effect (SME) and two-way
shape memory effect (TWSME). These last two are probably the best
known and they make very suitable this class of the materials for
innovative applications in various elds [13]. These remarkable
properties are controlled by a reversible structural transformation,
martensitic transformation, between the highly symmetric parent
phase (P) and the less ordered martensite (M) solid phases.
The shape memory effect is basically linked to a martensitic
transformation occurring in steels and several non-ferrous alloys.
By analogy with the martensitic transition of steels, the low temperature and high temperature phases of non-ferrous alloys are
called martensite (M) and austenite (A), respectively [1,4].
Several copper-based alloys have exhibited the shape-memory
effect and the understanding their characteristic thermal behaviors
and microstructure evolutions has brought a signicant impact on
their applications [5]. However, the shape memory effect (SME) of
the alloys is susceptible to aging whether in austenite phase (parent phase) or in martensite phase, which affects the applicability
of the alloys. There have been a lot of reports on the aging in parent

Corresponding author.
E-mail address: nbalo@rat.edu.tr (S.N. Balo).
0040-6031/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2012.02.007

phase of Cu-based SMAs [69]. The shape memory properties of

Cu-based SMAs are quite sensitive to alloying elements which are
added to adjust the martensitic transformation temperatures and
to optimize thermal stability as well as mechanical properties.
In addition, the martensitic transformation and the associated
mechanical shape reversibility in Cu-based SMAs are strongly
inuenced by quenching and aging treatments. The paper aims to
reveal aging effects in austenite of CuAlNi shape memory alloy. The
main experimental tool is differential scanning calorimetry (DSC)
which provided data for thermodynamic evolution of both forward
and reverse martensitic transformations. Thus, we have focused
on this study to know the effects of the thermal aging at a constant
temperature above Af on transformation and thermodynamics
parameters in a CuAlNi shape memory alloy.

2. Experimental
A ternary Cu-rich CuAlNi SMA with a nominal composition of
Cu13.5 wt.%Al4 wt.%Ni was supplied by Tremetaux, Centr de
Recherce (France). The samples cut from the alloy were annealed
in the phase eld for 20 min at 1203 K for betatization and rapidly
quenched in iced brine to obtained 1 martensite. The CuAlNi samples were aged for 1, 2, 3, 4, 5, 6 and 7 h above 50 K of the austenite
phase nish temperature (398 K). Aged alloy samples with various
periods were directly quenched in iced brine. The transformation
characteristics of un-aged sample and aged samples were examined by a Perkin-Elmer Sapphire model thermal analyzer at heating
and cooling rates of 10 K/min in the 303373 K range.

S.N. Balo, N. Sel / Thermochimica Acta 536 (2012) 15

Fig. 1. DSC curve of CuAlNi specimen annealed at 1203 K for betatization and rapidly quenched and un-aged.

X-ray diffraction measurements were carried out using a

Rigaku RadB DMAX II X-ray diffractometer with Cu-K radiation
The Vickers hardness measurements were perof  = 1.54056 A.
formed using an Anton Paar hardness tester machine. The samples
were tested with three indentations. The applied load was 15 gForce.
3. Results and discussion
The DSC curves of un-aged sample are shown in Fig. 1.
It is well known that SMAs undergo a thermally induced
austenite martensite transformation characterized by the critical temperatures; As , Af , Ms and Mf . Here As and Af refer to austenite
transformation start and nish temperatures, respectively, during
heating while Ms and Mf refer to martensite transformation start
and nish temperatures, respectively, during cooling. The transformation temperatures of the alloy are determined by tangent
method, as shown in Fig. 1. The transformation temperatures of the
alloy for various aging times and the corresponding latent heats of
phase transformations (enthalpy) are given in Tables 1 and 2. The
transformation temperatures As , Af , Ms and Mf of CuAlNi SMA are
increased with the thermal aging at rst 2 h, as seen in Table 1 and
Fig. 2 and they gradually are decreased for 5, 6 and 7 h. The increase
in thermal transformation temperatures with the thermal aging at
rst 2 h may be due to the instantaneous change entropy of the aged

alloy. The range of the phase change temperature varies with aging
and tends to decrease with increasing aging time. The hysteresis
width (Af Ms ) is varied by the thermal aging and generally tends
to increase with aging time. The obtained results suggest that the
transformation range of both (Ms Mf ) and (Af As ) is decreased by
the long-term thermal aging, since the thermal range of aged samples is narrower than that of un-aged sample, as seen in Table 1.
The Ms temperature is changed up to 7 K. Mf , As and Af temperatures also are shifted by the different amounts. This implies that
the hysteresis is changed, because the change in the transformation
temperatures Ms , Mf , As and Af is not the same for all the samples.
Also, it is well known that the difference in Ms Mf or Af As is related
to the stored elastic energy. Therefore, it seems worthwhile to analyze the thermal aging effects from a thermodynamical point of
view, which should be included into the discussion of the aging
effect above the austenite phase nish temperature on the CuAlNi
SMA.
The equilibrium temperature T0 between the martensitic and
the austenite phases is the temperature at which the Gibbs free
energies of the two phases are equal. Thus, the Gibss free energy
dependence of T0 temperature is expressed by the following relation,
GMA (T0 ) = GA (T0 ) GM (T0 ) = (H A T0 S A ) (H M T0 S M )
= H MA (T0 S MA )

(1)

The GM A Gibss free energy values for the various aging times
were calculated and are shown in Fig. 3. It is found that Gibbs free
energy is decreased by about 6% after 7 h thermal aging.

Fig. 2. Changes of transformation temperatures with various aging times in CuAlNi

alloy.

Fig. 3. Changes of GAM and Ge compared with the value of not aged sample.

S.N. Balo, N. Sel / Thermochimica Acta 536 (2012) 15

Table 1
The transformation temperature parameters of the alloy at various aging times.
Aging time (h)

Ms (K)

Mf (K)

Ms Mf (K)

As (K)

Af (K)

Af As (K)

Af Ms (K)

T0 (K)

0
1
2
3
4
5
6
7

350.9
350.7
353.4
348.3
350.2
345.3
344.1
343.9

331.7
327.8
336.1
329.5
335.2
332.6
332.1
329.3

292.2
295.9
290.3
291.8
288.0
285.7
285.0
287.6

341.3
344.4
347.0
340.9
347.1
343.8
343.4
340.6

358.5
361.1
363.5
354.2
359.5
355.5
354.5
352.6

290.2
289.7
289.5
286.3
285.4
284.7
284.1
285.0

280.6
283.4
283.1
278.9
282.3
283.2
283.4
281.7

354.7
355.9
358.4
351.2
354.8
350.4
349.3
348.2

Table 2
Aging effects on the thermodynamic parameters and Vickers Hardness of the alloy.
Aging time (h)

T0 (K)

HM A (kJ/kg)

SM A (J/kg K)

GA M (J)

Ge (J)

Average values of
Vickers hardness

0
1
2
3
4
5
6
7

354.7
355.9
358.4
351.2
354.8
350.4
349.3
348.2

9.15
7.22
8.32
8.69
9.06
8.84
8.41
8.88

25.79
20.28
23.21
24.74
25.53
25.22
24.07
25.50

0.095
0.095
0.106
0.070
0.115
0.123
0.124
0.101

7.347
5.424
6.192
7.118
7.212
6.905
6.805
6.791

725
736
837
801
595
518
597
701

Equilibrium temperature between the martensitic and

austenitic phases, T0 can be expressed by the following relation,
T0 =

1
(MS + Af )
2

(2)

In addition T0 for the alloy is expressed as [10]

T0 =

H MA
S MA

(3)

The hysteresis in the transformation is characterized by the driving force for the nucleation of martensite GAM (Ms ) as [1113]

after 6 h aging. The elastic strain energy is decreased by about 7%

after 6 h aging time and then 8% after 7 h aging time.
Also, we have aimed to investigate the role of long-term aging
above Af point on martensite characteristics and stabilization in
CuAlNi. For this purpose, X-ray diffraction patterns were taken from
alloy samples for various aging times, as shown in Fig. 5. These
diffractograms were taken from the alloy in as-quenched case (a),
after 2 h aging (b), after 4 h aging (c), after 7 h aging (d), respectively. The alloy has ordered structure in un-aged heat-treated case.
As seen in XRD patterns, the alloy exhibits a superlattice reection

GAM (Ms ) = GMA (T0 ) GMA (Ms ) = (T0 Ms )S MA (4)

The difference in Mf Ms is related to the elastic energy Ge stored
in self-accommodated martensitic variants by [11]
Ge = GAM (Ms ) GAM (Mf ) = (Ms Mf )S MA

(5)

where S MA entropy change and T0 is the equilibrium temperature between the martensitic and austenitic phases. As seen
in Table 2 and Fig. 4, the thermodynamic equilibrium temperature, T0 of the martensitic and the austenitic phases is increased
for 1 h and 2 h aging and then, is decreased with 4 h and up
aging times. The latent heat H MA of phase transformation and
S MA entropy values vary around 8.57 103 0.617 J/kg and
24.29 103 1.83 J/kg K respectively, as shown in Table 2. The elastic strain energy values Ge , for the samples were calculated and are
shown in Fig. 3. The elastic strain energy shows a minimum point

Fig. 4. Effect of various aging times on the equilibrium temperature of the alloy.

Fig. 5. X-ray piece diffractograms of CuAlNi shape memory alloy; (a) heat treated
and (b) aging at 2 h, (c) aging at 3 h (d) aging at 4 h, (e) aging at 7 h at 398 K after the
heat treatment.

S.N. Balo, N. Sel / Thermochimica Acta 536 (2012) 15

Table 3
Lattice Parameters according to aging time of the alloy.
Aging time (h)

a ()

b ()

c ()

a/b

0
1
2
3
4
5
6
7

4.2001
4.4433
4.1964
4.4498
4.1958
4.4958
4.4814
4.1804

5.1592
5.3826
5.1580
5.4069
5.1456
5.3153
5.3760
5.1604

38.6607
38.6207
38.8988
38.4020
38.5043
38.8157
38.4944
38.3599

84.19
85.41
84.07
84.82
84.42
85.32
92.92
86.48

0.8141
0.8255
0.8136
0.8230
0.8154
0.8458
0.8336
0.8101

in quenched case and even after 7 h aging. Miller indices which

has the atom distribution in the form of 18R structure refer to
the orthorombic unit cell of -type martensite. Indexed diffraction peaks show that the alloy has the orthorhombic 18R structure
in the martensitic condition and the diffraction patterns have been
indexed on the basis of orthorhombic unit cell. Thus, we have calculated lattice parameters using the following relation [14],
1
1
= 2
d2

h2
sin2

k2
1
+ 2
b2
c

l2
sin2

2hl cos
ac sin2

(6)

a/b ratios and lattice parameters of 18R martensite phase were calculated from the X-ray diffractograms
with aging duration are given
in Table 3. This ratio is less than 3/2 in the ordered case due to
atomic sizes of the constituent atoms for 18R martensite [15,16]. It
is evaluated that the X-ray results conrm a monoclinic 18R basis.
The changes in peak characteristics of the XRD patterns with aging
duration were investigated. Although all the XRD patterns exhibit
the similar characteristics, it was observed that the peak locations
of some diffraction planes were changed. Structure ordering is one
of the important factors for formation of martensitic [16,17]. It is
evaluated that the martensitic phase in Cu-based -phase alloys
is based on one of the (1 1 0) planes of austenite phase called
basal plane for martensite. A (1 1 0) plane in the -phase of DO3
(or L21 ) type ordered structure is rectangular, as in original case,
and it transforms to a hexagon with hexagonal distortion during
the martensitic transformation [18]. 18R is a metastable structure while the equilibrium structure of Cu13.5 wt.%Al4 wt.%Ni
shape memory alloy is formed from , and 2 phases. After 7 h
aging at 398 K, it is expectable that some atomic migration would
occur which would enable the precipitation of any of the above
equilibrium phases. This diffusion controlled phenomena would
alter the chemical composition of austenite, since we deal with
austenite aging, and this could explain the change in the critical
transformation temperatures. But if, it is evaluated that the entire
structure comprises only metastable 18R martensite, even after the
quenching of a 7 h-aged sample, this means there is no retained
austenite because it totally transformed into 18R martensite and
no marked uctuations of chemical concentration were observed
after quenching.
The crystallite size for the alloy was determined by the following
relation [19,20]
D=

0.9
b cos 

Fig. 6. Variation of crystallite size with various aging times.

(7)

where D is the crystallite size,  is the wavelength, b is the peak

broadening at full width at half maximum and  is the angle. The
crystallite size values for the samples aged various times were
determined and are shown in Fig. 6. As seen in Fig. 6, the crystallite
size is increased up to 3 h and indicates a maximum and then is
decreased with increasing time.
The change in crystallite size indicates the similar trend of transformation temperatures with a minimum for 3 h. This suggests
that the phase transformation parameters are controlled by the
crystallite size effect. It is evaluated that the increase in thermal

Fig. 7. Variation of Vickers hardness with various aging times.

transformation temperatures with the thermal aging at rst 2 h can

be due to the difference of their transformation strain.
The variation of Vickers hardness with various aging times is
shown in Fig. 7. The Vickers hardness of the alloy at rst 2 h is
increased by the aging at rst 2 h, as seen in Fig. 7 and then, is
decreased until fth hour. The hardness indicates an increase again
at sixth hour and seventh hour, as seen in Fig. 7 and Table 2. The
hardness value at seventh hour is near to value hardness of un-aged
sample. The change in hardness of the samples indicates that the
mechanical properties of the CuAlNi shape memory alloy can be
changed by the thermal aging effect.
4. Conclusions
The effects of the aging time on transformation temperatures
and thermodynamic parameters of the CuAlNi shape memory alloy
were investigated. A change in transformation temperatures was
observed due to thermal aging. It is found that the elastic strain
energy and Gibss free energy are decreased by about 8 and 6%
after 7 h aging time, respectively. The hardness value is increased
at rst 2 h aged and then at seventh hour is near to value hardness of un-aged sample. It was found that the phase transformation
parameters of the alloy are controlled by the crystallite size effect.
Acknowledgment
This study was supported by Firat University Research Fund
(FUNAF) under Project No. 1419.
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