Materials Science and Engineering A 521522 (2009) 182185

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Ageing effects after heat treatment in CuAlMn shape memory alloys

Agnieszka Mielczarek 1 , Nils Kopp 2 , Werner Riehemann
Institute of Materials Engineering and Technology, Clausthal University of Technology, Agricolastr. 6, D-38678 Clausthal-Zellerfeld, Germany

a r t i c l e

i n f o

Article history:
Received 31 May 2008
Accepted 7 October 2008
Keywords:
Shape memory alloy
CuAlMn
High damping
Aging
Phase transformation

a b s t r a c t
Different types of homogenization heat treatments, with homogenization temperatures varying from
800 to 920 C for 1 h and subsequently water quenching, were performed on CuAlMn shape memory
alloys with Al content 11.412.3 wt.% and Mn-content 5.06.9 wt.%. All homogenization heat treatments
of the investigated alloys lead to an increase of isothermal damping with increasing temperature. The
microstructure and phase fractions of the investigated samples depend on the homogenization temperature and cooling rate. The transition temperatures increased after every homogenization heat treatment.
Moreover, narrowing and increasing of the transformation peaks were observed by acoustic emission
measurements. Different martensitic transformations could be detected by acoustic emission measurements depending on the heat treatment. Strong and fast aging effects, decreasing the very high damping
capacities directly after all homogenization heat treatments were found in room temperature amplitude
dependent damping measurements. At least, there are three different possible explanations for the found
ageing effects in CuAlMn shape memory alloys: (1) pinning of twin and phase boundaries by point
defects diffusing to the boundaries during ageing, (2) partial phase transformation during ageing, (3)
decrease of the transformation temperatures.
2009 Elsevier B.V. All rights reserved.

1. Introduction
The main goal of the application of high damping materials is a
reduction of strong mechanical vibrations by energy dissipation. For
this purpose the material must provide high damping capacity often
found in polymers or other organic materials. If also good mechanical strength or good thermal or electric conductivities are needed
high damping metals (HiDaMets) can be applied. HiDaMets can be
developed from ferromagnetic metals using magneto-mechanical
damping, pure metals reinforced by high strength bres or particles, or martensiticaly transforming alloys, e.g. shape memory
alloys (SMA) [1]. The most investigated and utilized SMA are TiNi
and CuAlNi. These alloys are expensive and complex to produce
compared to CuAlMn SMA, developed in recent years [2,3].
Cast parts of CuAlMn SMA are inhomogeneous directly
after casting and should be homogenized at high temperatures
to improve their mechanical and damping properties. Homogenization heat treatments increase grain size, change transition
temperatures and phase composition, and therefore can substantially change the damping level of the CuAlMn SMA at application
temperature, e.g. room temperature [4,5]. For technical application

Corresponding author. Fax: +49 5323 723148.

E-mail address: werner.riehemann@tu-clausthal.de (W. Riehemann).
1
Now with: VW AG, Letter box 011/1499, 38436 Wolfsburg, Germany.
2
Now with: RWTH, IOT, Jlicher Strae 344a, 52070 Aachen, Germany.
0921-5093/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2008.10.066

high damping should stay stable for longer times after homogenization heat treatment contrary to previous ndings, showing severe
decrease of damping at room temperature after homogenization
heat treatment in CuAlMn SMA [4], called ageing. For this paper
the aging processes in CuAlMn alloys was investigated in more
detail. Aging in CuAlMn SMA is a very complex process due
to many possible martensitic phases. Below approximately 500 C
CuAlMn alloys have the ordered structure L21 (bcc), which transforms martensitically to 3R-fcc, 18R (small martensite plates) or 2H
(large martensite plates) structures [6,7] Additionally the aging processes, which can be caused by transformation, can lead to volume
changes, because during the transition from martensite to austenite
the lattice transforms from hexagonal or rhombohedral symmetry to body centred cubic crystal structure depending on the Mn
composition [8,9].
2. Experimental
The investigated alloys were obtained by melting copper
(99.99 wt.%), aluminium (99.7 wt.%) and manganese (99.85 wt.%) in
a mid-frequency induction furnace in normal atmosphere, followed
by casting in steel moulds preheated to 300 C. This state will be
always referred to an as cast state. The chemical compositions of
the alloys were determined by inductively coupled plasma spectroscopy (ICP) [10]. Specimens were thermally (heated or cooled)
treated and subsequently aged at different temperatures and times.
Normally, as aged without further description means heat treated

A. Mielczarek et al. / Materials Science and Engineering A 521522 (2009) 182185

Table 1
Names and chemical compositions of the investigated alloys.
Name

Cu in wt.%

Al in wt.%

Mn in wt.%

CuAl11.4Mn6.9
CuAl12.1Mn5.1

81.70
82.7

11.40
12.3

6.90
5.0

at 850 C for 1 h water quenched (w.q.) and aged for 2 years at room
temperature (RT).
In Table 1 the chemical compositions of the investigated alloys
are given. Transition temperatures are strongly dependent on the
treatment of the alloys and the transitions themselves are very
complex due to occurrence of many martensitic variants, therefore
they are not given in this table. The transition temperatures were
measured by acoustic emission. An acoustic 2 channel Acoustic
Emission Signal analyser (Physical acoustics Corporation, Princeton
Jct, USA) was used [10]. The temperature range of these measurements was 26 to 120 C. The cooling and heating rate was
20 K/min. The start transformation temperatures were dened by
the temperature when 100 acoustic events per second take place
during heating or cooling with this rate.
Internal friction versus maximum strain amplitude was measured at room temperature (RT = 22 C) in vacuum (10 Pa) as the
logarithmic decrement of free decaying bending vibrations of a
single clamped vibrating beam with a vibrating length of 97 mm,
a width of 10 mm, and a thickness of 2 mm. The specimens were
excited to resonant vibrations with resonant frequencies in the
range 3843 Hz depending on the mass of the beam and the mass at
the end of the bending beams. After stopping excitation, the decaying amplitudes were measured, and the strain dependent damping
calculated. More details about the used damping apparatus are
given in refs. [11,12].
3. Results and discussion
3.1. Recovery of the damping for as aged specimens
The amplitude dependence of damping for CuAl11.4Mn6.9, as
cast and heat treatment at 850 C for 1 h, has been reported in ref.
[4]. The amplitude dependence of damping increased signicantly
after this heat treatment. Some aging effects were reported, as well.
For the present work the same specimen was tested after approximately 2 years once again. The results are shown in Fig. 1. After 2

Fig. 1. Strain amplitude dependence of damping for CuAl11.4Mn6.9 after different

thermal treatments. Legend corresponds to the thermal treatment sequence top
down. w.q. = water quenched.

183

years the damping decreased and became much smaller than the
damping of as cast state for all measured strains. In ref. [4] it was
shown for the same specimen that during 120 days the damping
level after (1) homogenization at 850 C decreased to the damping
level of the as cast material. So, the aging process was not nished
after 120 days. After the damping measurement of as aged specimen two more homogenization heat treatments were performed
with this sample, (2) heat treatment at 800 C for 1 h and afterwards (3) heat treatment at 850 C for 1 h, both with subsequent
water quenching. The results show that all these heat treatments
could restore the damping properties after the rst homogenization
heat treatment as published in ref. [4] before 2 years. So ageing can
be recovered by homogenization heat treatments. As can be seen in
Fig. 1 after approximately 60 min the damping curve is on a similar
level as the damping of the specimen aged for 2 years. So ageing
always can be activated again after annealing at high temperature
like homogenization.
After ageing damping can be increased again by thermal treatments at low temperatures too. This can be seen in Fig. 1 for a
heat treatment at 150 C for 10 min, whereas heat treatments at
50 C and 100 C did not increase the damping again. The reasons
for this opposed effects of temperature at low temperature (ageing
below 150 C) and high temperature (restoration of high damping
above 150 C) could be kinetic (diffusion) and temperature dependence of thermodynamic equilibrium, respectively. More concrete
this could mean (1) that diffusing solid solutes to phase or twin
boundaries at low temperature causes ageing and that the evaporation of these atoms at higher temperatures causes restoration of
high damping. But this could also mean (2) that the phase transformation to austenite takes place between 100 and 150 C for aged
material. The reverse transformation in this case would occur during cooling and restore high damping before measurement at room
temperature. It is important to notice that between the third heat
treatment at 850 C and the rst damping measurements 30 min
are gone, so presumably the damping immediately after a suitable
heat treatment is much higher.
3.2. Ageing mechanisms and change of transition temperatures
Fig. 2 shows max , the height of the relative maximum in
the () curve at (c ) = max (compare with [4]), damping background 0 = ( = 0) and square of resonant frequency f2 against
increasing time during ageing obtained for different heat treated
CuAl12.3Mn5.0. It can be clearly seen that the heat treatment temperature has a big inuence on ageing. In particular the complete
aging of alloy CuAl12.3Mn5.0 heat treated at 920 C is maximum
(see Fig. 2a). The same heat treatment temperature dependence
shows the strain independent component of the logarithmic decrement 0 . The low damping of as cast state, marked by the horizontal
line in Fig. 2a, is due to a high austenite volume fraction in the
sample and a low grain size. It was already published [4,5,13] for
CuAlMn SMA that grain size can inuence the damping level.
In Fig. 2b the square of the resonant frequencies are plotted
versus ageing time after different heat treatments. Here an initial inuence of the homogenization temperatures can be observed.
The dimensions and weights of the specimens did not change during heat treatments. Therefore a measured resonant frequency is
directly proportional to the Youngs modulus for the variously heat
treated CuAl12.3Mn5.0 specimen. The initial (directly after heat
treatment) Youngs modulus decreases with increasing temperature of heat treatment while the initial strain independent damping
increases. Ageing leads to increasing Youngs modulus and decreasing damping whereas the nal values depend only weakly or not
detectable on the homogenization temperature. It is well known
that the Youngs modulus in SMA is higher in austenite than in
martensite, and is minimum, when stress-induced phase transfor-

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A. Mielczarek et al. / Materials Science and Engineering A 521522 (2009) 182185

Fig. 2. (a) relative maximum of logarithmic decrement max (i.e. peak in ()) curve
and damping background 0 versus ageing time in log-log-plot, and (b) f2 versus
ageing time of CuAl12.3Mn5.0 after different heat treatments for 1 h.

mations can occur within the temperature range MF < T < MD (above
MD no stress-induced transformation can take place) [14].
Homogenization heat treatments and ageing processes inuence not only the microstructure but also the transition
temperatures. Martensitic transition is an acoustic active process
and can be detected by acoustic emission measurements (see [15]).
In Fig. 3 the acoustic events per second for heating and cooling
of CuAl12.3Mn5.0 after different heat treatments are plotted ver-

sus temperature. Heating and cooling runs are shown in different

grey-scales. The occurring peaks indicate phase transitions during
heating or cooling, respectively. Depending on the heat treatment
up to tree peaks corresponding to tree phase transitions clearly separated by their transition temperatures could be detected. It is well
known for CuAlMn alloys and identied by X-ray measurements
that austenite can be transformed to more than one martensite
type or one martensite type can successively transform to an other
[6,7,12]. The acoustic emissions measurements show that at least
two different martensite types are produced. Moreover there are
indications of even tree martensitic types. This third phase transformation could be acoustically measured only during the heating
run after heat treatment at 920 C/1 h (see Fig. 3-peak X in heating run). This additional peak disappeared with increasing aging
time at RT. Every AE measurement was made twice and the peak X
was reproducible. Additionally, all acoustic emission peaks shift to
higher temperatures with increasing aging time. No changes were
found in optical micrographs after aging.
The found ageing effect (i.e. decrease of damping after homogenization heat treatment) can not be explained by a slowly
isothermal transition of martensite back to austenite like it was
assumed as a possibility for explanation in [4], because of the
present acoustic emission results, where it can be clearly seen
that peaks, which indicate martensitic transformations, shift to
higher temperatures, i.e. specimens become more martensitic or
the martensitic state is stabilized at room temperature. The most
probable reason for such strong aging effects is the isothermal
stabilization of martensite by pinning of phase and twin boundaries by point defects like vacancies or solute atoms. An additional
evidence for this explanation could be that thermal treatment at
150 C restores the high damping level. But his recovery can also
be explained by austenitic transformation during heating between
100 and 150 C and back transformation to martensite due to water
quenching. Cesari et al. stated [16] that the existence of mobile
point-like defects is controlled by the stoichiometry of the shape
memory alloys based on CuAl alloy type.
4. Conclusions
The temperature of the homogenization heat treatment inuences seriously the damping and ageing properties of CuAlMn
SMA. Different types of phase transformations as well as different transition temperatures could be detected by acoustic emission
measurements depending on the heat treatment. There are still
two different possible explanations for the found ageing effects in
CuAlMn shape memory alloys: (1) pinning of twin and phase
boundaries by point defects diffusing to the boundaries during ageing, and (2) partial phase transformation during ageing to various
martensite types. Here pinning of phase and twin boundaries is
more probable because isothermal transformation to martensitic
variants could not be detected.
Acknowledgments
The authors are thankful to Prof. Babette Tonn and Dipl.Ing. Snke Vogelgesang (IMet, Clausthal University of Technology,
Germany), who provided the cast samples and the acoustic emission apparatus. This work was nancially supported by Deutsche
Forschungsgemeinschaft (DFG).
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Fig. 3. Temperature dependence of acoutstic active events during heating and

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heat treated 850 C/6 min/w.q., (3) heat treated 950 C/6 min/w.q., (4) 420 h at room
temperature, (5) heat treated 920 C/60 min; w.q. = water quenched.

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