Materials Science and Engineering A 438–440 (2006) 782–786

Thermo-mechanical characterization of Cu–Al–Ni shape memory

alloys elaborated by powder metallurgy
A. Ibarra a,∗ , J. San Juan b , E.H. Bocanegra a , M.L. Nó a
aDepartamento de Fı́sica Aplicada II, Facultad de Ciencia y Tecnologı́a, Universidad del Paı́s Vasco, Apdo 644, 48080 Bilbao, Spain
b Departamento de Fı́sica Materia Condensada, Facultad de Ciencia y Tecnologı́a, Universidad del Paı́s Vasco, Apdo 644, 48080 Bilbao, Spain
Received 13 June 2005; received in revised form 16 November 2005; accepted 25 December 2005

Abstract
Some years ago a new powder metallurgy process was developed for the elaboration of Cu–Al–Ni shape memory alloys in order to overcome
drawbacks observed in samples produced by conventional casting. This method introduced improvements in the mechanical and thermo-mechanical
alloy properties; however, it has not permitted an accurate control of the composition and, in turn, of the transformation temperatures of the alloys.
An additional step, mechanical alloying, was introduced to have a better control of this parameter. This work presents the characterization of the
alloys obtained by the improved method. In comparison with samples produced by other methods, indications of a similar thermo-mechanical
behaviour (super-elastic and pseudo-elastic effect) were observed for these samples.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Shape memory alloys; Cu–Al–Ni; Powder metallurgy; Mechanical alloying; Thermo-mechanical properties

1. Introduction new step, mechanical alloying, was introduced in the elaboration

Cu–Al–Ni alloys are being investigated as preferential can-
didates for applications up to 240 ◦ C [1]. These applications are
based on their thermo-mechanical features like the super-elastic
or pseudo-elastic properties, the two-way shape memory effect
and the high damping [2]. However, poly-crystals of this sys-
tem produced by conventional casting are quite brittle [3] and
it is necessary to improve their mechanical behaviour in order
to guarantee the reliability required for technological applica-
tions. In addition, the technological applications of these alloys
need an accurate control of the composition, because slight vari-
ations in Al concentration produce strong modifications in the
transformations temperatures [4]. Against this background, it is
necessary to develop a new fabrication method, which provides
the required transformations temperatures, without losing their
thermo-mechanical properties.
Cu–Al–Ni shape memory alloys obtained by powder metal-
lurgy show better mechanical and thermo-mechanical properties
than polycrystalline samples obtained by other methods [5]. But
some drawbacks were detected. To overcome these drawbacks a
∗ Corresponding author. Tel.: +34 94 601 5437; fax: +34 94 601 3500.
E-mail address: wdbybgaa@lg.ehu.es (A. Ibarra).
process [6]. The alloys produced by the improved method have
been investigated with the purpose of testing the enhancement
in the thermo-mechanical properties.
2. Experimental methods
A Cu–13.65 wt.% Al–3.3 wt.% Ni polycrystalline alloy was
produced by the powder metallurgy processing method pro-
posed in [5] which has been improved by the introduction of the
mechanical alloying step [6]. The complete process is schemati-
cally outlined in Fig. 1. Starting from pure elements, by melting
and alloying, two alloys with different composition were elab-
orated. Both alloys were atomized using Ar gas. The powders
were mixed in an appropriated rate in order to obtain the desired
composition. Subsequently, the mixture was alloyed mechani-
cally for 15 h and compacted by hot isostatic pressing. The bulk
sample was then cut and hot-rolled as described in Ref. [6]. The
rolling creates a new texture in the sample [7,8]. Afterwards,
three tensile samples (A, B, C) were spark-machined from the
poly-crystal sheet. The sample cross-section was 5 mm × 1 mm
and the gauge length was 25 mm between two shoulders for grip.
Finally, the samples were annealed at 1173 K for 1800 s in an
argon atmosphere, quenched in a mixture of ice and water, and
aged at 453 K for 24 h in an oil bath. The final product consists

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.12.053
 A. Ibarra et al. / Materials Science and Engineering A 438–440 (2006) 782–786 783

of martensite phase. The surfaces were mechanically polished

after the thermal treatments to remove the oxide layer.
In order to characterise the thermal behaviour of the alloy, dif-
ferential scanning calorimetry (DSC) was performed in a Perkin-
Elmer DSC Pyris1. In addition, thermo-mechanical effects have
been investigated using a 4467 Universal Instron test machine
at a constant deformation velocity 6.67 × 10−4 s−1 . The tensile
cycles were performed at different temperatures in an Instron
Temperature Chamber 3119-006. The sample strain was mea-
sured using an Instron extensometer clipped to them.
The martensitic transformation was investigated by optical
microscopy using a Leica DMR optical microscope. The sam-
ples were mechanically polished in martensite phase at room
temperature and, subsequently, heated in the optical microscope
with a lincam TMS92 cooler/heater slide, to obtain the parent
phase. When the reverse transformation occurs, an inverse relief
appears in the ␤-phase surface, corresponding to the previous
plates presented in the sample before heating. In order to empha-
size the contrast of this relief the samples were observed by
means of interferential contrast and two crossed-polarizers.

3. Experimental results

In order to check the correspondence between transforma-

Fig. 1. Powder metallurgy elaboration process, improved with the new step,
mechanical alloying [5,6].
tion temperatures and alloys composition [9], a thermal cycled
was measured by means of DSC. Fig. 2a shows the thermogram
measured in the alloy after the thermal treatments. Both forward
and reverse transformations can be observed in the correspond-
ing cooling and heating cycle. A metallographic study was made

Fig. 2. DSC curves. (a) Thermogram of the sample just after the thermal treatments. (b) Thermograms of the sample strained up to 4.5% with a residual deformation
of 0.8%.
784 A. Ibarra et al. / Materials Science and Engineering A 438–440 (2006) 782–786

Fig. 4. Pseudo-elastic effect at room temperature until 2.5% maximum defor-

mation.

Fig. 3. Metallographic study of martensite plates. The original pictures were

taken in colour by means of interferential contrast. (a) Sample just after thermal
treatment. The plates do not cross the grain boundaries. (b) Sample that shows Fig. 5. Super-elastic effect to 4.5% maximum strain at different temperatures.
TWSME. The martensite plates can cross the grain boundaries.
the sample is heated at a temperature higher than 140 ◦ C. After
to investigate the macroscopic characteristics of the martensite these thermo-mechanical cycles, it has been observed a two-way
plates. Fig. 3a shows a representative micrograph where grain shape-memory effect (TWSME) during thermal cycles. There-
boundaries (GB) of the parent-phase can be observed clearly, as fore, a new DSC thermogram (Fig. 2b) has been performed, in
well as the martensite plates.
Once the thermal martensitic transformation has been con-
firmed, the thermo-mechanical properties have been checked.
Fig. 4 shows a pseudo-elastic cycle in sample A at room tempera-
ture. After unload, a residual deformation remains in the sample.
This deformation disappears completely when the sample is
heated up to a temperature at which the reverse transformation
is completed (one-way shape-memory effect). The super-elastic
effect has been tested in samples B and C. Fig. 5 shows the
stress–strain (S–S) curves at three different temperatures (100,
110, 140 ◦ C) up to 4.5% maximum deformation. The residual
deformation will be discussed below. Fig. 6 shows the super-
elastic cycles performed at 110 ◦ C, in sample C, with different
maximum deformation. Five cycles have been performed from
0.5 to 2.5% maximum strain. A last cycle up to 4.5% maximum
strain, which retains 0.8% remaining deformation after unload-
ing the sample, was applied. This deformation disappears when Fig. 6. Super-elastic effect at 110 ◦ C and different maximum deformation.
 A. Ibarra et al. / Materials Science and Engineering A 438–440 (2006) 782–786
the 4.5% strained sample, to find out the cause of this residual
deformation and the complete recover of it. The changes in the
martensite plates microstructure were investigated using optical
microscopy in order to explain the TWSME (Fig. 3b).
4. Discussion
Fig. 2a shows the martensitic transformation during a ther-
mal cycle. In the reverse transformation, according to Ref. [9]
two kinds of martensite ␤ and ␥ must have appeared in a sam-
ple with this composition. In fact, using optical microscopy two
kinds of martensites have been observed (Fig. 3a). The trans-
formations temperatures measured for this alloy are Ms : 54 ◦ C,
Mf : 44 ◦ C, As : 62 ◦ C, Af : 77 ◦ C. These values are higher than the
transformation temperatures reported in Ref. [9] for a single-
crystal alloy with the same composition. However, Recarte et
al. have shown how the transformation temperatures shift up
when the sample has been aged [10]. The high transformation
temperatures determined for this sample correspond well with
the shift predicted by these authors.
In both pseudo-elastic and super-elastic S–S curves
(Figs. 4–6) the slope corresponding to the martensite transfor-
mation is not horizontal like in the case of single crystals. The
presence of differently oriented grains justifies this positive slope
in the pseudo-elastic and super-elastic curves for the martensitic
transformation.
Fig. 4 shows a pseudo-elastic cycle carry out at room tem-
perature up to 2.5%. The residual deformation disappears when
the sample is heated up to the ␤-phase. Therefore, this figure
shows that the grain boundaries do not prevent neither plates
reorientation nor re-transformation to the parent phase.
The super-elastic effect is characterised by the alloy
behaviour as a function of the sample temperature and of the
maximum deformation reached. Both parameters have been
investigated. The effect of the temperature is shown in Fig. 5.
When the sample temperature increases, σ c shifts up, as pre-
dicted by the Clausius-Clapeyron equation for the shift of the
first order transformations temperatures when an external stress
is applied. In the latter case, Fig. 6, a downfall in σ c is observed
in every cycle with respect its previous one. The critical stress
necessary to induce the transformation shifts from 160 MPa in
the first cycle to 120 MPa in the fifth one. So the stress, which
constrains the martensitic nucleation, is reduced in every cycle.
In spite of this, there is an increase of the slope at 3.5%, which is
probably linked to a higher stress necessary for the plate growth
close to the grain boundaries or crossing them, see Fig. 3b.
Just once reached this percentage of strain; residual deforma-
tion keeps in the sample after unload completely.
DSC showed in Fig. 2b, which has been carried out in a sam-
ple strained up to 4.5%, shows three different peaks in the first
heating. The first one represents the ␤ → ␤-transformation, the
second one is the re-transformations of the ␥ -martensite, and the
third is the disappearing of some stabilised martensite plates.
Similar results have been observed in Ref. [11] for stabilised
martensite in single crystals. The values of H measured in
every peak show that whereas for the second peak remains con-
stant in both cycle (H = 0.189 J/g) for the first one increases its
785
value from H = 3.51 to 4.19 J/g when the third one disappears.
So, we can conclude that the plates stabilised re-transformed to
␤ -martensite when the sample is cooled again. The stabilisation
of the martensite (residual deformation) just appears after the
change of the slope (Fig. 6), probably this is associated with the
highest stress necessary for plate growth due to the presence of
GB as obstacles for this growth. The presence of these handicaps
can produce an increase of the parallel dislocation density [12].
These new dislocations can produce the decrease observed in σ c ,
the stabilised martensite and the TWSME observed. The reason
is that they can induce plates with the same direction, in relation
to the external stress, although they have different orientation
with respect to the crystallographic directions in every grain, or
they can promote the plates to cross small-angle GB. Fig. 3b
shows the optical observation on the “trained” sample. Just two
preferential growth directions of the plates can be observed and
the plates seem to pass through the grains boundaries.
5. Conclusions
The advantages of a new powder metallurgy fabrication
method were tested. The thermal martensitic transformation has
been checked at the expected temperatures. The martensites
obtained were those expected according to the literature. With
respect to the thermo-mechanical properties, indications of a
better thermo-mechanical behaviour (super-elastic and pseudo-
elastic effect) has been observed for these samples, than those
observed in other alloys produced by powder metallurgy. The
transformation can be induced, without any crack in the sam-
ple, at a temperature almost 70 ◦ C higher than Af and the alloys
can support stress higher than 400 MPa. σ c is reduced in every
cycle. The stress during the forward transformation shifts up
from 3.5%, probably due to the necessity of higher stress to come
close the boundaries and these handicaps produce an increase of
dislocations density close to them. This modification can gener-
ate TWSME.
Acknowledgements
This work is supported by the MCYT project MAT
2000-1676-C02-01 and MAT2004-03166, “Accion Integrada”
HF 2003-0187 (Picasso Programme), “Grupos Consolidados”
UPV/EHU UPV00063.310-13646/2001 and the Basque Coun-
try Government Project ACTIMAT from program ETORTEK.
A. Ibarra would like to acknowledge MCYT for his grant Ref.
FP 2000-5940.
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