Materials Science and Engineering A273 275 (1999) 625 629

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Characterization of a hot-rolled CuAlNiTi shape memory alloy

C. Segu a,*, J. Pons a, E. Cesari a, J. Muntasell b, J. Font b
a

Departament de Fsica, Uni6ersitat de les Illes Balears, Carretera de Valldemossa, km 7.5., E-07071 Palma de Mallorca, Spain
b
Departament de Fsica i Enginyeria Nuclear, Uni6ersitat Polite`cnica de Catalunya, Diagonal 647, E-08028 Barcelona, Spain

Abstract
The changes in the martensitic transformation of a CuAlNiTi alloy hot-rolled at different temperatures have been studied
in detail, covering different aspects such as ageing in the parent phase at temperatures ranging between 250 and 350oC,
stabilisation of the martensite and betatization of the previously hot-rolled specimens. Besides the evolution of transformation
temperatures upon different thermal treatments, special attention has been paid to the changes in mechanical properties of the
alloy, such as elastic modulus and internal friction. These results are analysed in relation to the microstructural changes as
observed by transmission electron microscopy. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Martensitic transformation; Shape memory alloys; CuAlNiTi; Thermal treatments; Mechanical properties

1. Introduction
A considerable interest exists towards shape memory
alloys transforming above 100oC, because of their
prospective applications. Among the Cu-based shape
memory alloys, the CuAlNi system offers the best
potential because of the high transformation temperatures that can be chosen while maintaining a better
thermal stability than for CuZnAl. However, polycrystalline CuAlNi displays a poor ductility which
can be improved by grain refinement as achieved
through Ti and/or B additions.
Ageing in the parent phase of CuAlNiTi alloys
leads to the formation of the g2 phase which, together
with the Ti-rich X-phase [1], affect the martensitic
transformation characteristics and specially the mechanical properties such as the internal friction (IF) and
elastic modulus (E). As a matter of fact, it has been
found that the presence of X-precipitates, which are not
affected by ageing, decrease the IF maximum occurring
during the martensitic transformation; this fact has
been explained by the decreasing mobility of the parent/martensite interfaces due to grain boundaries and
fine dispersion of X precipitates [1 3]. As for the
g2-phase precipitates, they are known to increase the
* Corresponding author. Tel.: +34-971-173224; fax: + 34-971173426.
E-mail address: dfscsp0@ps.uib.es (C. Segu)

transformation temperatures due to Al depletion of the

matrix [4], but its influence on the IF and E behaviour
is largely unknown. Apart from the ageing effects both
in b and martensite, the production processes like hotrolling can influence the martensitic transformation undergone by those alloys.
In this paper we study the martensitic transformation
of a CuAlNiTi alloy hot-rolled at different temperatures. The effects of the rolling temperature will be
described, as well as the behaviour of the differently
hot-rolled alloys upon ageing both in parent and
martensite phases.

2. Experimental procedure
A polycrystalline alloy with a nominal composition
Cu -11.9% Al- 4.8% Ni- 1.0% Ti (wt.%) (nominal Ms of
100oC) was used in this study. Several ingots of the
alloy were hot-rolled in the same conditions at different
temperatures in the range between 600 and 850oC, but
a systematic study was performed on those hot rolled at
850 (alloy A) and 650oC (alloy B), which were representative of significantly different behaviours. Specimens of
those alloys were subjected to ageing at different temperatures in the parent and martensite phases performed in a melted salt bath. The martensitic
transformation was monitored by means of differential
scanning calorimetry (DSC; Perkin-Elmer DSC7) and

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C. Segu et al. / Materials Science and Engineering A273275 (1999) 625629

626

Table 1
Transformation characteristics of as-received alloys A and B; the transformation heat Q is averaged over the cooling and heating runs and IFmax,
IFint and DE/E correspond to the heating run

Alloy A
Alloy B

Mp (oC)

Ap (oC)

DT (K)

Q (J/g)

IFmax

IFint (K)

DE/E

108
164

130
193

22
29

7.9
6.9

0.15
0.08

0.29
0.32

0.27
0.08

dynamic mechanical analysis (DMA; Perkin-Elmer

DMA7) working in a three point bending configuration. Details on the last mentioned technique can be
found elsewhere [5]. Transmission electron microscopy
(TEM) observations of samples in different conditions
was performed using a Hitachi H600 100 kV microscope, the thin foils being prepared by double jet electropolishing in 30% nitric acid in methanol at 240 K.

3. Results and discussion

3.1. Comparison of hot-rolling at different temperatures

Throughout the present work, the DSC peak temperatures obtained on cooling (Mp) and heating (Ap) will
be taken as representative of the martensitic transformation temperatures. As it can be seen in Table 1, the
as-received alloy A shows lower transformation temperatures, a lower hysteresis and a larger transformation
heat than as-received alloy B. Similarly, the IF maximum (IFmax) and the relative modulus minimum (evaluated as DE/E= (Em Emin)/Em, where Em stands for
the modulus value in the martensite phase and Emin is
the modulus minimum) occurring during the martensitic transformation are lower in the as-received alloy B
compared to alloy A, but the transformation in the
former is spread over a wider temperature range and,
hence, the integrated IF (IFint) has similar values for
both rolling temperatures.
The microstructure of the alloys at room temperature
shows a martensitic matrix (18R structure) with intra
and intergranular micrometer sized particles. In alloy
A, the particles were identified from the selected area
electron diffraction patterns as being X-phase (type XL)
[4], whereas in alloy B, in addition to the XL particles,
g2 particles were also identified, both having similar
sizes and undefined shapes, and being incoherent with
the martensitic matrix. Fig. 1 shows the microstructure
of alloy B. The grain size is slightly smaller for alloy B
(5 10 mm) than for alloy A (15 20 mm). It is interesting
to notice that, for the present composition and according to x-ray diffraction experiments, the temperature of
650C corresponds to the g +b region, while 850C lies
inside the single b phase region. The complicated microstructure of the alloys at room temperature, having
a large number of interfaces between very small

martensite plates which contain stacking faults, hide the

contrast of the dislocations introduced by rolling. When
observing in parent phase condition (after in situ heating above the Af temperature), the presence of similar
low density dislocation distributions in both as-received
alloys is revealed. Thus, the influence of the rolling
temperature on the transformation properties is predominantly due to the precipitation of the g2 phase in
alloy B during rolling. In fact, after betatization (30
min at 850C), TEM observations confirmed the dissolution of the g2 particles in alloy B and both alloys
showed a transformation behaviour very similar to the
as-received alloy A. When treated for 30 min at 650C,
specimens of both alloys showed a transformation
spread over a very large temperature range with very
low transformation heat, due to the decomposition of
the b phase.

3.2. Ageing in the parent phase

As shown in Fig. 2(a), ageing alloy A in the b phase
leads to an increase of both the forward and reverse
transformation temperatures, Mp increasing by less
than Ap thus widening the transformation hysteresis
DT = (Ap Mp). The same effects occur in shorter
times the higher the ageing temperature. The transformation heat remains constant up to 60 h ageing at
250oC, but starts to decrease after 5 h at 300oC or 30
min at 350oC. For alloy B, Ap increases upon ageing at
250, 300 or 350oC (although to a lesser extent than

Fig. 1. Microstructure of as-received alloy B at room temperature.

C. Segu et al. / Materials Science and Engineering A273275 (1999) 625629

627

Fig. 2. Ap, Mp and DT as a function of ageing time at different temperatures for alloy A (a) and B (b).

alloy A), but Mp shows a small increase followed by a

decreasing tendency, causing a sharp increase in hysteresis (see Fig. 2(b)). The transformation heat starts to
decrease after 48 h ageing at 250oC, 5 h at 300oC or
about 5 min at 350oC.
As can be seen in Fig. 3(a) and (b), IFmax decreases
with increasing ageing time at 250oC for both alloys.
Similarly, DE/E progressively diminishes with increasing ageing time at 250oC until its apparent disappearance, which occurs after about 20 h for alloy B and 60
h for alloy A. This is also shown in Fig. 4(a) and (b).
Specimens of alloy A aged for 5 min, 30 min and 3 h at
350C were also studied by means of DMA, a sharp
decrease on IF values and modulus minimum taking
place upon ageing and no transformation occurring
after 3 h ageing.
The microstructural changes occurring during ageing
at 250oC have been followed by TEM, a slow decomposition process being observed in both alloys. At the
beginning (i.e. up to 10 h ageing at 250oC), the images
show a very finely mottled contrast, but after more
prolonged ageing (50 and 85 h) small precipitates with

sizes of few nm can be distinguished, forming a dense

dispersion throughout the samples (Fig. 5) (a very
similar process as that reported in [6]). These precipitates are more densely accumulated at the B2 and L21
antiphase boundaries. Due to their very small size, no
extra diffraction spots could be observed, but they are
believed to be most probably of the g-type phase. For
the alloy B, in addition to this fine precipitation,
growth of the big g2 particles already present in the
as-rolled condition has been observed. Ageing at 350C
caused the same fine precipitation process being developed at much shorter ageing times (for instance, the
images observed after 30 min at 350C in alloy A are
very similar to that obtained after 85 h at 250C).
Nevertheless, after a more severe ageing of alloy A (30
min at 400C), the fine precipitates did not grow further
(they had the same size as for 30 min at 350C) but,
instead, big particles of g2 phase (mm sized) were observed, many of them near the XL particles.
Improvement of the L21 short range order, together
with the effects of the fine precipitation process observed by TEM are the more feasible causes for the

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C. Segu et al. / Materials Science and Engineering A273275 (1999) 625629

increase of Ap, Mp and DT upon moderate ageing. The

small precipitates influence the transformation in two
different ways: a chemical effect (change of composition of the matrix) and a non-chemical effect related to
the difficulties in the martensite/precipitate accommodation. However, the latter effect would bring about a
decrease of transformation temperatures, as indeed observed in CuZnAl containing small g precipitates
[7,8]. Thus, in the present case, the non-chemical effect
seems to be overcompensated by the compositional
effect as well as by the short range ordering taking
place upon ageing. The degradation of transformation
characteristics observed after a severe ageing can be
related to the development of the big g2 particles in
both alloys.
As for the DMA results, the lower IF peaks and less
pronounced modulus minimum as well as the larger
temperature spread of the IF peaks in alloy B are
thought to be a consequence of the big g2 precipitates
always present in this alloy, while the finely dispersed
precipitates are held responsible for the observed decrease during ageing at 250C. A decrease in the IF
peak values could arise from a decrease in transformed
mass fraction since, as a first approach, the IF values
depend on the amount of transformed mass in a stress
oscillation cycle performed at each temperature. Never-

Fig. 4. IF and E modulus spectra obtained during heating after 5 min

and 65 h ageing at 250oC for alloys A (a) and B (b) (runs performed
at 1 Hz, 5 K min 1 and stress amplitude 4 MPa).

theless, the fact that the transformation heat (which is

considered to be proportional to the amount of transformed material) remains constant, except for the
severely aged alloys, allows to discard this possibility as
a general rule. Because the IF peak during the martensitic transformation is due to the hysteretic movement
of the parent/martensite interfaces [10], the decrease in
IF is attributed to the decreasing mobility of these
interfaces caused by the precipitated particles; the big
ones (XL and g2) cannot be overcome by the growing

Fig. 3. IF peak values and relative modulus minima as a function of

ageing time at 250oC for alloys A (a) and B (b).

Fig. 5. Dark field image of the small precipitates observed in a sample

of alloy A aged 85 h at 250C.

C. Segu et al. / Materials Science and Engineering A273275 (1999) 625629

Fig. 6. Reverse transformation temperature shift, Ap(1)-Ap(2), as a

function of ageing time in martensite.

parentmartensite interfaces, causing a considerable reduction of the martensite plates size, while the small
precipitates are actually absorbed by the martensite
plates when they grow, a process which is energetically
expensive due to the accommodation of precipitates in
the martensite phase [8], and then limits the displacement of the interfaces during the oscillating stress. The
enlargement of the transformation temperature range
caused by precipitation of g2 and the decrease in strain
per oscillating cycle caused by the poor mobility of the
interfaces are responsible for the progressive disappearance of the E-modulus minimum.

629

to martensite ageing. The shift is the higher the longer

the ageing time and the higher the ageing temperature,
as seen in Fig. 6.
CuAlNi alloys are less prone to martensite stabilisation than CuZnAl ones, and indeed, no noticeable
stabilisation occurred in any of the alloys upon ageing
up to 110C, a temperature at which a high martensite
stabilisation is usually observed in CuAlZn alloys.
However, stabilisation actually takes place in the studied alloys if ageing is performed at higher temperatures.
This fact can limit the application of these alloys at
very high temperatures. It is also interesting to emphasize that, for CuZnAl it has been established that
dense distributions of small g precipitates inhibit
martensite stabilisation by ageing at room temperature
[9], while it seems not to be the case for the dense
dispersion of very small precipitates present in the
studied CuAlNiTi alloy after ageing, although in
this comparison, the very different ageing temperatures
have to be taken into account.

Acknowledgements
The authors acknowledge the partial financial support received from the DGES, research project PB950340.

References

3.3. Ageing in martensite

Specimens of both alloys A and B were subjected,
either in the as received condition or after one transformation cycle, to different ageing stages in the martensitic state, up to 2 months at 90 and 110C, no
appreciable shift in the reverse transformation temperatures being observed in any case. Specimens of alloy A
were first aged for 30 min at 350oC, in order to increase
their transformation temperatures allowing martensite
ageing at higher temperatures (150, 200 and 210C).
The first reverse transformation measured after ageing
displays a significant shift in transformation temperatures with respect to the second reverse transformation,
which recovered the transformation temperatures prior
.

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