Materials Science and Engineering A 378 (2004) 278–282

Characteristics of Cu–Al–Mn-based shape memory alloys

and their applications
Y. Sutou a , T. Omori a , J.J. Wang b , R. Kainuma a , K. Ishida a,∗
a Department of Materials Science, Graduate School of Engineering, Tohoku University, Aoba-yama 02, Aoba-ku, Sendai 980-8579, Japan
b School of Materials & Metallurgy, Northeastern University, 3-11, Wenhua Road, Shenyang, Liaoning 110006, PR China

Received 26 November 2003; received in revised form 26 November 2003

Abstract

Recent progress on ductile Cu–Al–Mn-based shape memory alloys (SMAs) is presented. The various properties of superelasticity (SE),
the shape memory effect (SME), the two-way memory effect (TWME) and internal friction are enhanced by controlling grain size and texture
through thermomechanical treatments. It is also shown that the control of stress-induced martensitic transformation due to cold-rolling of
Cu–Al–Mn SMAs results in low thermal expansion (LTE). In addition, the medical application of the Cu–Al–Mn-based SMAs to guidewire
is introduced.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Shape memory alloys; Cu–Al–Mn; Superelasticity; Grain size; Texture; Damping; Guidewire

1. Introduction exhibit SME and SE based on cubic ␤1 (L21 ) to ␤1 (6M)

Shape memory alloys (SMAs) such as Ni–Ti-based,
Cu-based and Fe-based alloys are commercially attractive
for the practical applications of superelasticity (SE), the
shape memory effect (SME) and the two-way memory
effect (TWME), and are drawing attention as high damp-
ing materials. Among these alloys, the Cu-based SMAs
which are lower in cost than the Ni–Ti-based alloys and
show better SME and SE than the Fe-based alloys are the
most attractive alloys for practical applications. However,
the polycrystalline Cu-based SMAs such as Cu–Al–Ni and
Cu–Zn–Al are too brittle to be sufficiently cold-worked
due to the high degree of order and high elastic anisotropy
in the ␤-parent phase [1,2]. Attempts have been made to
improve the ductility of these polycrystalline Cu-based
SMAs, mainly by grain refining, with limited success
[1,3].
Kainuma et al. have found that the Cu–Al–Mn alloys with
a low Al content less than 18 at.% show excellent ductil-
ity because their parent phase with an L21 structure pos-
sesses a low degree of order [4,5]. Moreover, these alloys
martensitic transformation [4,5]. However, SME and SE
strains are less than 2%, which is not sufficient for practi-
cal applications in many fields. Very recently, the present
authors have demonstrated that SM characteristics such as
SE, SME and TWME, and the degree of internal friction in
Cu–Al–Mn-based SMAs can be enhanced by the addition of
alloying elements and the application of microstructure con-
trol achieved by thermomechanical treatment [6–11]. Espe-
cially, it has been clarified that those characteristics strongly
depend on grain size and the development of texture. In ad-
dition, Kainuma et al. have also demonstrated that low ther-
mal expansion (LTE) can be obtained in Cu–Al–Mn-based
SMAs by controlling stress-induced martensitic transforma-
tion due to cold-rolling [12,13].
In this paper, we present recent progress on Cu–Al–Mn-
based SMAs with high SM characteristics, high internal fric-
tion and LTE by microstructure control and their application
to medical parts.
2. Effect of grain size on SE property

∗ Corresponding author. Tel.: +81-22-217-7321;

It is known that SM characteristics depend on the grain
fax: +81-22-217-7321. size relative to the size of a specimen, such as sheet
E-mail address: ishida@material.tohoku.ac.jp (K. Ishida). thickness, t, sheet width, w, wire diameter, D, etc. [14].

0921-5093/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2003.12.048
 Y. Sutou et al. / Materials Science and Engineering A 378 (2004) 278–282
10 2 1
(a) d/D=0.05 7 (c)
6
400 5 (b)
MAX (%)
4
(b) d/D=0.42 3
εSE
2
300
Stress (MPa)
1 (a)
III II
00 1 2
(d/D)-1/2
200
(c) d/D=4.54
100
0 εSE
0 2 4 6
Strain (%)
Fig. 1. Tensile stress–strain curves in: (a) the (Cu72 Al17 Mn11 )99.8 –B0.2
specimen with d/D = 0.05; (b) the Cu72 Al17 Mn11 specimen with
d/D = 0.42 and; (c) the (Cu72.5 Al17 Mn10.5 )99.5 –Co0.5 specimen with
d/D = 4.54, where d and D indicate grain diameter and the diameter of
the wire specimen, respectively. The inset shows the εMAXSE vs. (d/D)−1/2 ,
where εMAX
SE was obtained from the cyclic-tensile testing [6,8,9].
Fig. 1 shows the stress–strain curves of wire specimens of
Cu–Al–Mn-based SMAs, where d indicates the grain diam-
eter. Tensile testing was carried out at Af + 30 ◦ C at a strain
rate of 0.5 mm/min. Specimens with different d/D were
prepared using various thermomechanical treatments [9]. It
is seen that the SE property strongly depends on the d/D
and that the SE strain, εSE , increases with increasing d/D.
As shown in the inset in Fig. 1, the maximum SE strain,
εMAX
SE , is plotted by a Hall–Petch-type relation as a function
of (d/D)−1/2 , where εMAX SE was obtained by cyclic-tensile
testing, the method of which has been previously described
in detail [6,8,9]. It is seen that the εMAX
SE plots are divided
into three regions (I, II and III) depending on the d/D. In
the specimens in region III, a SE strain of about 7%, which
is nearly equal to that of Ni–Ti SMAs, can be obtained,
while the specimens in region I show SE strain of about
2%. In region II, εMAXSE abruptly increases with increasing
d/D. These results can be explained from the standpoint
of constraint strain among the grains [9]. Since the grain
structure in specimens changes from a fine grain structure
(region I) to a bamboo-like structure (region III) via a
columnar-like structure (region II) with increasing d/D, the
constraint strain from the surrounding grains in the speci-
mens changes from three- to one- via the two-dimensional
mode and may be released, especially in region II
which corresponds to the transition region of the strain
mode.
3. Effect of texture on SE property
Since the SE strain of single crystal SMAs strongly de-
pends on the loading direction, control of texture is ef-
fective for enhancing SE strain in polycrystalline SMAs.
279
d/D
0.2 0.1
I
3 4
8
Fig. 2. Tensile stress–strain curves in the loading direction RD, 45◦ from
RD and TD of the (Cu73.5 Al17 Mn9.5 )97 –Ni3 textured sheet, where RD,
45◦ from RD and TD are defined in the inset. The tensile stress–strain
curve in the Cu71.5 Al17 Mn11.5 sheet with random texture is also shown.
The stereographic triangle shows the texture property in each specimen.
The present authors have previously found that a strong
{1 1 2}1 1 0 recrystallization texture can be obtained by
the addition of Ni and through thermomechanical processing
(TMP), where annealing in the fcc (␣) + bcc (␤) two-phase
region followed by heavy cold reduction of over 60% and
final solution-treatment of over 900 ◦ C are conducted [8,9].
The enhancement of texture due to the addition of Ni would
be related to the increase in the volume fraction of the ␣
phase at the annealing temperature [8]. Fig. 2 shows the
stress–strain curves obtained for specimens cut along the
loading directions RD, 45◦ from RD and TD in the sheet
specimen with the {1 1 2}1 1 0 texture, where the direction
of RD, 45◦ from RD and TD, is defined as shown in Fig. 2,
including the stress–strain curve of a specimen with random
texture. The stereographic triangle which indicates the tex-
ture property of each specimen is also shown in Fig. 2, where
these specimens have the values d/t = 1.2 and d/w = 0.08.
It is seen that the SE property strongly depends on the load-
ing direction. The SE stain of the specimen in the 45◦ from
RD is the highest, while that of the specimen in the TD
is lowest. The SE strain of the specimen in the RD is al-
most equal to that of the specimen with the random texture.
Such orientation dependence of the SE strain for the tex-
tured specimens is in good agreement with the anisotropy
of transformation strain for single crystal predicted from the
calculation based on the phenomenological theory [8]. The
SE strain of the textured sheet specimen also depends on
the relative grain size d/t and d/w, and a large SE strain of
7.5% can be obtained in the {112}110 textured specimens
with d/t = 3.2 and d/w = 0.2 at the 45◦ from RD [9]. This
value may be the largest of all the Cu-based SMAs with
polycrystalline structure.
280 Y. Sutou et al. / Materials Science and Engineering A 378 (2004) 278–282
4. Improvement of SME and TWME by control of
grain size and texture
The SME which is one-way memory effect depends on the
relative grain size and the development of texture as well as
on the SE strain. A large recoverable strain can be obtained
in a specimen with a large relative grain size, as well as in a
textured specimen cut along the loading direction 45◦ from
RD [9].
The remarkable TWME due to the high deformation
method without training in Cu–Al–Mn-based SMAs are
also obtained by controlling the relative grain size and the
texture [9,10]. In this study, TWME tests were performed
by bending a sheet specimen into a round shape at room
temperature followed by heating up to 200 ◦ C and cooling
down to −196 ◦ C. Fig. 3(a) shows the TWME strain εtw
versus the applied surface strain εa in the specimens with
various relative grain size d/w, where the d/t of all spec-
imens was almost one and the Ms temperatures of those
specimens was nearly equal to −10 ◦ C. The εtw obtained
for Cu–Zn–Al SMAs is also shown in Fig. 3(a). In all spec-
imens, the obtained εtw increases with increasing applied
surface strain εa in the initial stage and then decreases after
reaching a maximum. These results suggest that there is
an optimum amount of slip defects to obtain the highest
εtw in each specimen. It can be seen that the maximum
εtw increases with increasing d/w. An excellent value of
Fig. 3. (a) TWME strain, εtw vs. applied surface strain εa in the
Cu72 Al17 Mn11 specimen with various d/w, where w is the width of sheet
specimen. The εa dependence of the εtw for Cu69.5 Zn24.5 Al6 SMA is also
shown; (b) the dependence of εa on the εtw in the (Cu73.5 Al17.5 Mn9 )97 –Ni3
specimen with different texture.
εtw = 2.8% is obtained in the specimen with d/w = 0.46
deformed up to 16.4%, while only a εtw less than 1% in the
Cu–Zn–Al with d/w = 0.32 can be obtained by deforming
up to 5% because the Cu–Zn–Al SMA is cracked at the
grain boundary by bending deformation over 5%. Fig. 3(b)
shows the effect of texture on the εtw in the specimens with
d/w = 0.13, where the Ms temperatures of those specimens
were −42 ◦ C. Similar to the case of SE strain, the εtw de-
pends on the texture and the highest εtw of 3.6% can be
obtained in the specimen cut along the 45◦ from RD, while
the specimen in the TD shows the lowest εtw .
Omori et al. have also clarified from in situ observations
of the surface relief that an excellent TWME can be ob-
tained by the growth and contraction of the specific variant
stress-induced by the bending deformation [10]. In addition,
under the deformation at room temperature, εtw is depen-
dent on Ms and the specimen with Ms ≈ −100 ◦ C shows
the highest value of εtw [7,10].
5. Damping property of Cu–Al–Mn-based SMAs
Recently, SMAs are drawing attention as high damping
materials with high tensile strength. Fig. 4 shows the tem-
perature dependence of the value of dynamic damping tan
φ when the Cu–Al–Mn-based SMAs wire with d/D = 0.08
and 1.86 are heated. It is equal to that of internal friction of
those specimens. The measurement of tan φ was carried out
by tensile-testing using a dynamic mechanical spectrometer
(DMS), where the frequency and the strain amplitude used
DMS measurement were 1 Hz and 5 × 10−4 , respectively
[11]. In both the specimens, the tan φ abruptly increases
with the reverse transformation, and the tan φ in the marten-
site phase is higher than that in the austenite phase, where
these characteristics can be also obtained in cooling condi-
tion, i.e., martensitic transformation. The degree of the tan φ
increases with increasing d/D. Particularly, in the specimen
0.4
d/D=1.86
d/D=0.08
0.3 Ni-Ti-based
tan φ
0.2
0.1
0
-150 -100 -50 0 50 100
Heating Temperature (˚C)
Fig. 4. Temperature dependence of tan φ in the (Cu72.9 Al17 Mn10.1 )99.3 –
Co0.5 B0.2 specimen with d/D = 0.08 and the Cu72 Al17 Mn11 specimen
with d/D = 1.86, and in the Ni50.8 Ti49.2 specimen.
 Y. Sutou et al. / Materials Science and Engineering A 378 (2004) 278–282
with d/D = 1.86, the tan φ drastically increases with the re-
verse transformation and reaches a value of about 0.37 at the
temperature of the martensite + austenite two-phase region.
These results imply that the mobility of the habit plane and
twin boundary increase with increasing d/D, which is equiv-
alent to a relaxation of the grain constraint. On the other
hand, the tan φ of the Ni–Ti-based SMAs is less than 0.1,
although the peak width of the tan φ extends over 100 ◦ C.
Details of the microstructure dependence on the internal fric-
tion of Cu–Al–Mn-based SMAs will be reported in the near
future.
6. Low thermal expansion (LTE) induced by
cold-rolling deformation
Kainuma et al. have recently demonstrated that an
Invar-type effect can be obtained in some SMAs by
controlling the stress-induced martensitic transformation
due to cold-rolling [12,13]. Fig. 5(a) shows thermal ex-
pansion curves in the rolling direction (RD) obtained
from as-cold-rolled Cu71.5 Al18 Mn10.5 alloy, where the
cold-rolling was applied at a temperature over the Af . The
thermal expansion curves of pure Cu and Fe–40.5 Ni Invar
alloy are also shown in Fig. 5 for comparison. It can be
seen that shrinkage of the specimen during heating, that
is, negative thermal expansion due to the reverse transfor-
mation, is enhanced by cold-rolling in the low reduction
(a) Cu
Pure
Fe-40.5Ni
10%
8%
∆l/l
5%
2 10-3 1%
0%
20
(b)
15 Pure Cu
CTE (10-6 /K)
10 8%
5 in Fig. 6(b). It can be seen that the tip of the guidewire
0
-5
-100 -80 -60 -40 -20 0 20 40 60 80 100
Temperature (˚C)
Fig. 5. (a) Thermal expansion curves in the rolling direction of the
as-cold-rolled Cu71.5 Al18 Mn10.5 specimens compared with those of pure
Cu and Fe–40.5 Ni alloys. The reduction rate from the initial thickness
is shown by a percentage on every curve; (b) temperature dependence of
CTE of 8% cold-rolled Cu–Al–Mn specimen and pure Cu.
281
region, while a high reduction over several percent points
results in a decrease of the transformation shrinkage and the
almost zero thermal expansion can be obtained in the spec-
imen cold-rolled up to 8%. Fig. 5(b) shows the coefficient
of thermal expansion (CTE) versus temperature in the 8%
cold-rolled specimen. The CTE of that specimen shows a
value within (−2 to 4) × 10−6 at the temperatures ranging
about from −40 to 40 ◦ C. On the other hand, the trans-
verse direction (TD) and the normal direction (ND) of the
as-cold-rolled specimen show positive thermal expansion,
that is, an anisotropy of the thermal expansion property
exists. This result suggests that this LTE phenomenon is
essentially caused by anisotropy of displacement due to
stress-induced martensitic transformation. Actually, it was
confirmed from X-ray measurement at room temperature
that the martensite phase induced by cold-rolling has a
crystallographic anisotropy where the (200)6M , (006)6M
and (020)6M are roughly parallel to the RD, TD and ND
sections, respectively [12,13]. These results apparently
mean that the most suitable martensite variant to release the
stresses applied by cold-rolling are preferentially induced
during deformation and stabilized in the high temperature
region over the Af temperature. This phenomenon can be
explained as a kind of TWME.
Such LTE characteristics can be obtained in other SMAs
such as Cu–Zn–Al, Ni–Ti and Ni–Al alloys. Moreover,
Kainuma et al. have also demonstrated that two-dimensional
LTE with LTE ≈ 0 in every direction of the sheet plane can
be obtained by alternate cross-rolling [12,13].
7. Application of Cu–Al–Mn-based SMAs
Since the Cu–Al–Mn-based SMAs show excellent duc-
tility and high SM characteristics as mentioned above,
their application in various fields is highly expected. Here,
we briefly introduce the application of Cu–Al–Mn-based
SMAs to medical guidewire as an example. Fig. 6(a) shows
a guidewire with a diameter of 0.5 mm which is coated
with resin and whose tip is angled to improve its maneuver-
ability in branched blood vessels. This Cu–Al–Mn-based
guidewire has a unique characteristic, i.e., a functionally
graded characteristic which can be obtained by control-
ling the microstructure. Fig. 6(b) shows the dependence of
the length of the guidewire from the tip on the bending
load σ f and shape recovery which are defined in inset (B)
shows excellent flexibility and SE property which are
obtained by control of the relative grain size, while the
end of guidewire shows high stiffness and strength and
hardly exhibit the SE property. Furthermore, those prop-
erties gradually vary in the range from 100 to 500 mm.
Such enhancements of the stiffness and strength are caused
by bainitic transformation induced by aging at around
200–400 ◦ C [15]. The graded properties can be obtained
by aging treatment using a furnace with a temperature
282 Y. Sutou et al. / Materials Science and Engineering A 378 (2004) 278–282
Fig. 6. (a) Cu–Al–Mn-based guidewire with functionally graded property;
(b) the dependence of the length from the tip of guidewire on the bending
load σ f and the shape recovery. Inset (A) shows the load-deflection curves
in each portion of the length from the tip of guidewire. The σ f and the
shape recovery rate are defined in inset (B).
Fig. 7. Cu–Al–Mn-based SMA tubes with dimensions: (a) φ
1.0 mm × φ 0.85 mm and; (b) φ 0.6 mm × φ 0.5 mm. The inset shows the
SE property of tube (a).
gradient. This guidewire with functionally graded prop-
erties shows excellent pushability and torqueability [15].
These graded properties realized by microstructure con-
trol cannot be achieved in the other guidewires of Ni–Ti
and stainless steels. This Cu–Al–Mn-based guidewire is
now under evaluation by doctors. Cu–Al–Mn-based SMAs
can be easily fabricated not only as sheets and wires,
but also as tubes and thin foils because of their supe-
rior ductility. Fig. 7 shows Cu–Al–Mn-based SMA tubes
with dimension of (a) φ 1.0 mm × φ 0.85 mm and (b) φ
0.6 mm × φ 0.5 mm. The inset in Fig. 7 shows the ten-
sile stress–strain curve of tube (a). It can be seen that
this Cu–Al–Mn-based SMA tube shows a good SE prop-
erty. These micro-tubes are expected to be used not only
in medical equipment, but also in various other practical
applications.
8. Conclusion
Cu–Al–Mn-based SMAs have an excellent ductility and
show excellent SM characteristics and a high damping prop-
erty due to microstructure control such as grain size and
texture control. Furthermore, the LTE characteristic can be
obtained by control of stress-induced martensitic transfor-
mation. The present Cu–Al–Mn-based SMAs have high po-
tential for practical applications as SE, SME and TWME
component materials and high damping material and the
LTE material with high thermal and electrical conductivi-
ties in medical and electrical devices, micromachines and
energy-storage technological applications.
Acknowledgements
This work was supported by the Grant-in-aids for Sci-
entific Research from the Ministry of Education, Science,
Sports and Culture, Japan.
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