January 1998

ELSEVIER Materials Letters 33 (1998) 291-296

Effect of parent phase ageing on CuZnAl shape memory alloys

with Mn and Zr addition
C.Y. Chung a~*,C.W.H. Lam a, S.S. Tan b
a Department of Physics and Materiuls Science, City University of Hong Kong, 83 Tat Chee At)enue, Kowloon, Hong Kong
b Department of Materials Science and Engineering, Central South Unk~ersity of Technology, Changshrc 410083, Hunan, China

Received 3 December 1996; revised 25 April 1997; accepted 25 April 1997

Abstract

The effect of parent phase ageing on CuZnAl and CuZnAlMnZr shape memory alloys was studied. It was found that
re-ordering took place during parent phase ageing for the CuZnAl alloy. When the ageing temperature reached 2OO”C,
bainite started to precipitate and further ageing resulted in decomposition to the equilibrium phases. The consequence was a
drastic drop in shape memory capacity and the decrease of transformation temperatures by solute depletion. With the Mn and
Zr addition, bainitic precipitation and decomposition were also found. However, the re-ordering phenomenon was not
significant when the ageing temperature was below 200°C where there was no change in shape memory capacity. 0 1998
Elsevier Science B.V.

Kewordst Shape memory alloys; Parent phase ageing; Martensitic transformation: CuZnAl alloy

1. Introduction have been many attempts to refine the grains by

adding elements such as Zr, Ti, V and Cr [2].
Cu-based shape memory alloys (SMA) are con- The purpose of the present paper is to investigate
sidered economical alternatives to NiTi-based the change in the degree of order during parent phase
SMA’s. Nowadays, many commercial products are ageing and compare the thermal stability of the
made from Cu-based alloys. However, martensite CuZnAlMnZr alloy with the CuZnAl alloy. The
stabilization and parent phase ageing are problems microstructural evolution during ageing was fol-
that badly affect shape memory performance. SMA’s lowed until the alloys decomposed into their equilib-
are usually exposed to thermo-mechanical cycling rium phases. As soon as the controlling factors of
and high temperatures. Therefore, the study of parent thermal stability are better understood, a shape mem-
phase ageing is essential to our understanding of the ory alloy with higher shape memory capacity may be
thermal stability problem. Moreover, Cu-based designed.
SMA’s also suffer from a low ductility problem [1]
and poor mechanical properties due to their intrinsic
large grain sizes and high elastic anisotropy. There 2. Experimental methods

The Cu-21Zn-6Al wt% (alloy A) and Cu-

* Corresponding author. 2lZn-6Al- lMn-0.5Zr wt% (alloy B) shape mem-

00167-577X/98/$19.0 0 1998 Elsevier Science B.V. All rights reserved

P/I 30167-577X(97)001 I I-O
292 C.Y. Chmg ct d./Materiuls Letters 33 (IYYKI 2!?-296

ory alloys were prepared by melting elements with l”)l (a)

industrial purity in an induction furnace. The ingots
were hot rolled to 1 mm plates. Powders were filed
from the plates and iron debris was removed from
the SMA powders using a magnet. The SMA pow-
o
0

2
a,
cF--2+oyA
80~
60

ders were then sealed in copper foils for ageing E

d 40,
treatments. Plate samples were cut into small pieces E
for DSC (differential scanning calorimeter) analysis. F
20
All the samples were betatized at 820°C for 5 min
and then quenched into boiling water. They were oL .____. I
kept at 100°C for 30 min and cooled with the water 0 20 40 60 80 loo 120 140 160 180 200

to room temperature. These samples were aged at 70, Ageing Temperature ‘C

100, 150, 200 and 300°C in an oven for 6 h. X-ray

diffraction analysis using the powder method was 75 (b)

carried out in Siemens D-500 X-ray diffractometer.

Alloy A
DSC analysis was done in a Perkin-Elmer DSC7 60

thermal analyzer. The heating and cooling rate were =i m I 45

+ 20 and - 20”C/min, respectively. Micrographs B
-q
were taken in an optical microscope and a JEOL-820 2
E 30)
SEM. The samples were mechanically polished and w
etched with 5 g FeCl, + 10 ml HCl + 100 ml H ?O 15

solution.
00
I
0 20 40 60 80 100 120 140 160 180 200

Ageing Temperature ‘C
3. Results
Fig. I. DSC results for alloys A and B after ageing at different

Fig. 1 depicts the result of thermal analysis. Fig.
la shows the change in the peak temperatures of the
forward and reverse martensitic transformations of
alloys A and B after ageing at different temperatures.
The transformation temperatures decreased slightly
when the alloys were aged below 100°C. Larger
drops were found for alloy A when aged at 150°C.
After ageing at 200°C no martensitic transformation
could be found in alloy A; however, it was still
present in alloy B. Transformation enthalpies were
calculated by integrating the area of the DSC trans-
formation peaks. Fig. I b shows the change of en-
thalpy in the forward martensitic transformation with
respect to ageing temperatures. The enthalpies were
not changed much after ageing at a temperature
below 150°C but dropped more significantly after
ageing at 200°C. This implies that the volume of
transformable parent phase decreases when ageing
temperatures are high enough. The parent phase
could either have stabilized or decomposed into other
phases. This phenomenon is more severe in alloy A
than in alloy B after ageing at 200°C as the volume
temperatures (a) peak temperatures during reverse (Ap) and for-
ward (Mp) transformations. (b) transformation enthalpy in forward
transformation.
of transformable parent phase in alloy A has dropped
to zero. Both alloys show no martensitic transforma-
tion after ageing at 300°C.
From the XRD results, the martensite structure of
the step quenched sample was M18R for both alloys.
Parent phase was also present as a minor component.
The amount of parent phase increases with an in-
crease in the ageing temperatures. Corresponding
increases in the equilibrium phases, the a phase and
p phase, were also found. Splitting parameters from
the (122),-(202),, (lZlO>,-(?OlO), and (040),-
(320), line pairs were calculated using Eqs. (la),
(1 b) and (lc) and plotted in Fig. 2.
p, = sin’ fI(T22) - sin2 Q(202) (la)
p? = sin’ 0( 1210) - sin’ H(ZOl0) (lb)
pi = sin’ 0(040) - sin’ 8(320) (Ic)
 C.Y. Chung et al./ Materials Letters 33 (19981 291-296 293

25(4 drop. However, the splitting parameters of alloy B

were not changed much. The q and x-parameter
were also calculated based on the XRD results using
Eqs. (2) and (3). They are shown in Table 1 together
with the lattice parameters.

cp=2tan~’ !- (2)
i 2a i

1
"0 20 40 60 80 IW 120 140 160 180 200
x=-+ ; cos p
Ageing Temperature ‘C 3 i 1

25
r? The XRD results for alloy A can be summarized in
0 :b) /.\
-- the following trends: (i) pl, p2, p3 --) 0; (ii> /3 +
x (0 4 0) (3 2 0)
20
90°C; (iii) cp--) 60” and (iv) x + l/3. These trends
: imply that the M 18R martensite changed from M 18R
; I5 to N18R structure upon ageing. For alloy B, the
H--z
(1210)-(-2010)
changes in these parameters were less obvious when
2 10
P
aged below 150°C. The transformation enthalpies
._
E -1 a were almost constant. Nevertheless, the transforma-
E 5
(-1 2 2) (2 0 2) tion enthalpy was lowered in samples aged at 200°C.
fn

Figs. 3 and 4 show the microstructure of alloys A

0
0 20 40 60 80 100 120 140 160 1'30 200 and B before and after ageing. The grain size of
Ageing Temperature ‘C CuZnAl was about 300 pm. With the addition of
Fig. 2. Change of splitting parameters with respect to ageing Mn and Zr to CuZnAl, we found that both the
temperatures for (a) alloy A and (b) alloy B. equiaxed grain and martensite plates were refined.
The grain size was reduced to about 75 pm. The
microstructure of alloy B cannot be easily revealed
by optical microscopy because the martensite plates
The splitting parameters of alloy A drop steadily and microscopic features were very fine. A typical
with increasing ageing temperatures. The higher the martensite morphology can be found in step quenched
ageing temperature, the more severe became the and 70°C aged samples, as shown in Fig. 3(a) and

Table 1
Lattice parameters for alloys A and B after different thermal treatments
Alloy Ageing (“C) Lattice parameters P” cpO x

a (nm) b (nm) c (nm)

A S.Q. 0.4423 0.5298 3.8183 88.802 6 I X36 0.3534
70 0.4432 0.5295 3.8213 88.762 61.705 0.3540
100 0.4430 0.5304 3.8178 88.955 61.813 0.3508
150 0.4448 0.5289 3.8330 89.150 61.466 0.3475

B S.Q. 0.4416 0.5308 3.8 185 88.69 1 62.011 0.3553

70 0.4420 0.5318 3.8219 88.633 62.061 0.3563
100 0.442 1 0.5317 3.8241 88.634 62.040 0.3562
150 0.4425 0.5322 3.8241 88.742 62.042 0.3544
294 C. Y. Chung et 01. /Mr~rritrls Lrtteu 3.3 (1 YYKl 201-296

Fig :. 3. Microstructure of alloy A after different thermal treatment (a) as-quenched. (b) 70°C agein g, (c) IWC ageing, (d) 200°C ageing and
(e) 300°C ageing.

Fig 4. Microstructure of allay B after different thermal treatment (a) as-quenched. (h) 70°C ageing, (c) 150°C ageing, (d) 200°C agelng and
(e) 300°C ageing.
 C.Y. Chung et al./Materials
(b). After ageing at 150°C for 6 h, some substruc-
tures perpendicular to the martensite/martensite in-
terfaces were found, Fig. 3(c). Bainite was found in
all 200°C aged samples (Fig. 3(d) and Fig. 4(c)). (Y
(bright) and p (dark) equilibrium phases can be
readily seen after 300°C ageing. In comparison, Fig.
4 shows that a typical martensite structure appeared
in the step quenched alloy B as well as the aged
samples. Bainite precipitated after ageing at 200°C
and only 30% transformable martensite remained.
Ageing alloy B at 300°C led to the formation of a
large area of (Y and p phases.
4. Discussions
Ageing is always a problem in Cu-based shape
memory alloys. The metastable martensite and parent
phase formed from both directly quenched and step
quenched /3 phase can be easily stabilized by the
time-dependent diffusional process during ageing.
Disordering of atoms usually accompanies the diffu-
sion. From the XRD spectra of alloy A, the changes
in cp, x-parameter and splitting parameters indicate a
transformation from Ml 8R to N18R upon ageing.
Such a transformation is a consequence of the order-
to-disorder atomic diffusion process. The basal plane
of the ordered thermoelastic martensite cannot be
closely packed into a regular hexagon as the ordered
Cu, Zn and Al atoms have different radii. Therefore,
the adjacent layer cannot fit exactly in the l/3
position. This results in a monoclinic structure. In
alloy A, cp and p were found to tend to 60 and
90°C respectively, and x decreases towards l/3
during the course of ageing. The alloy showed a
tendency to disorder and formed a normal 18R struc-
ture (N18R). This kind of disordering is inherited
from the parent phase since the alloy is aged above
A,. A similar behavior was also observed by Gui et
al. [3] in martensite ageing.
Although disordering takes place during ageing
between 70 and 150°C in alloy A, there is no obvi-
ous decrease in the corresponding transformation
enthalpy, as shown in Fig. lb. Drops in enthalpies
were found only when the samples were aged at
200°C or above. This implies that the order-to-dis-
order transformation has not affected the ability of
the thermoelastic parent phase to transform when the
Letters 33 (1998) 291-296 295
ageing temperature is kept at 150°C or below. How-
ever, we believe that when the ageing temperature is
raised to 200°C or above, the further lowering of the
degree of order, or the increase of disorderness,
might affect the transformation more significantly.
Such lowering of degree of order will change the
crystallographic relationship between the parent and
martensite phase. Martensitic transformation will then
be inhibited, and subsequently the shape memory
capacity will be reduced.
Fig. 3(d) and Fig. 4(c) reveal that bainite starts to
precipitate after 200°C ageing. This is a transition
phase that will ultimately transform to (Y phase as
reported for the p-CuZn alloy [4]. After 300°C age-
ing, much larger regions of (Y and p phase were
found. Since cy phase is Al-depleted, the Al concen-
tration in the matrix will be increased. This will alter
the chemical composition of the parent phase and
reduce the amount of transformable parent phase.
The lowering of transformation temperatures shown
in Fig. 1 conforms to this argument.
The purpose of adding Zr to CuZnAl is to control
the grain size. Zr-rich secondary phase was found
uniformly distributed in the sample[5]. The transfor-
mation temperatures were lowered by Mn addition,
as shown in Fig. 1. The splitting parameters of alloy
B are also larger than those of alloy A. This implies
that the degree of order of alloy B is higher. It has
been suggested [6] that an increase in the degree of
order can facilitate the transformation because a
lower misfit strain is needed to be accommodated at
the martensite/austenite interface. Hence the trans-
formation temperatures are lower.
We can see that after alloy B has been aged at or
below 150°C for 6 hours, the changes in splitting
parameters, cp and x-parameter are less obvious than
those found in alloy A. The ageing kinetics has been
changed by adding Mn and Zr. The disordering
process is then suppressed. The addition of Mn and
Zr may increase the binding force between the con-
stituent atoms because the change in the degree of
order is a diffusional process. Hence, the activation
energy for diffusion is increased and the diffusion
rate of atoms for re-ordering would also be lowered.
In ordinary CuZnAl alloys such as alloy A, direct
quenching (DQ) usually results in stabilized marten-
site which cannot show any thermoelastic martensitic
transformation. The reason for stabilization has been
attributed to the clustering of quenched-in vacancies
on some closely packed (OOI), planes, causing the
neighboring lattice planes to be distorted and form-
ing partial dislocation or else producing sessile dislo-
cation loops by the collapse of vacancies [7]. These
factors contribute to a decrease of ordering and act
as impediments to the movement of atoms in the
reverse martensitic transformation. In CuZnAlMnZr
SMA, we expect that the quenched-in vacancy con-
centration should also be high in the DQ samples. If
the diffusion rate in the DQ CuZnAl and CuZ-
nAlMnZr are the same, the DQ CuZnAlMnZr should
also have the martensite stabilization problem. How-
ever, martensite stabilization is not observed in the
DQ CuZnAlMnZr. Both the forward and reverse
martensitic transformations were recorded in the DSC
thermal analysis. This indicates that the diffusion
rate for atoms and vacancies in CuZnAlMnZr might
be lower. We suggest that the addition of Mn and Zr
has inhibited the activities of vacancies by lowering
their diffusion rate in both the martensite stabiliza-
tion and the parent phase stabilization processes. The
consequence is a lower decomposition rate for alloy
B. This also explains the higher thermal stability of
alloy B upon ageing.
To summarize, re-ordering takes place during par-
ent phase ageing. Instead of transforming to the
Ml8R martensite, the re-ordered parent phase trans-
forms to martensite with a structure closer to Nl8R.
The shape memory property of the near Nl8R
martensite is similar to that of the M18R martensite.
The parent phase will not be stabilized until a certain
degree of disorder is reached. This stabilization is
controlled by the ageing temperature and time. With
prolonged ageing at high temperatures, such as 200°C
for 6 h, precipitation starts to take place and destroys
the thermoelastic martensitic transformation. The
parent phase transforms to other phases such as
bainite and LYphase. This decreases the transforma-
tion temperatures of the remaining martensites by
solute depletion. On the other hand, the addition of
Mn and Zr has lowered the diffusion rate of the
constituent atoms and suppressed the rate of disor-
dering. Although there is no significant enlargement
of the temperature range where the parent phase is
stable as the bainitic precipitation starts to take place
when aged at 200°C for 6 h, the alloy behaves in a
more stable manner than ordinary CuZnAl alloy
when aged below 150°C. Moreover, addition of Zr
can also reduce the grain size, while addition of Mn
can lower the transformation temperatures by in-
creasing the degree of long range order.
Acknowledgements
The authors gratefully acknowledge the financial
support provided by the City University of Hong
Kong. This investigation is funded by the CityU
Strategic grant No. 700275. Particular thanks are due
to Dr. W.H. Zou for her valuable discussions and
Mr. S.M. Tang for his help in the experimental work.
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