Materials Science Forum Vols 453-454 (2004) pp 187-192 Online: 2004-05-15

© (2004) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/MSF.453-454.187

Aging Effects in Cu-Zn-Al Shape Memory Alloy

V. Asanovi , K. Deliji and Z. Leka

Faculty of Metallurgy and Technology, Podgorica, Serbia and Montenegro

Keywords: Aging Kinetics, Cu-Zn-Al Shape Memory Alloy, Shape Memory Recovery

ABSTRACT

The effects of quenching and aging treatments on the structure, properties and precipitation
kinetics in a Cu-22.3Zn-5.1Al (wt%) shape memory alloy have been investigated. The martensitic
transformation temperature, MS, during isothermal aging from 200 to 4000C decreases with aging
time at each aging temperature. Aging at 4000C significantly reduces the tensile ductility and yield
strength of this alloy. The periods of isothermal aging required to initiate precipitation of -phase
have been examined at various temperatures, and a time-temperature-transformation (TTT) diagram
is drawn. The apparent activation energy estimated from the loss of shape memory recovery is
similar to the activation energy of -precipitation in the alloy.

1. INTRODUCTION

More than 60 years went by since the first observation of the shape memory effect and 40
years since the phenomenon has attracted worldwide attention with the announcement of shape
memory in an alloy of nickel and titanium. A family of shape memory alloys based on copper, zinc
and aluminum was developed in the 1970’s. Because these ternary alloys are much cheaper than the
Ni-Ti ones and much easier to machine and fabricate, they are of particular interest, for example for
the production of couplings, springs and actuators.
The application of martensitic Cu-Zn-Al alloys in shape memory devices requires a stable
and reliable transformation temperature to attain a mechanical action at the designed temperature.
To fulfill the function of a memory device it is also important that transformation during thermal
extrusions does not reduce the capacity of the device. Many researches have reported degrading
effects of aging in martensite and parent phases of Cu-Zn-Al alloys [1-11]. The stabilization of Cu-
Zn-Al martensite was found to be a thermally activated process that could be reduced by a step-
quenching treatment [4, 5, 7]. Up-quenching treatment was also proposed for solving the room-
temperature aging problem of Cu-Zn-Al martensite [12].
In the present work the precipitation and its kinetics in a Cu-22.3Zn-5.1Al [wt%] alloy were
investigated in order to increase the service life of shape memory capacity in the alloy.

2. EXPERIMENTAL

The alloy, Cu-22.3wt%Zn-5.1wt%Al, was melted in a graphite crucible under protective

charcoal cover using a resistance-heated furnace. The melt was poured into a graphite mould of 14
mm x 65 mm x 100 mm, previously heated at 1200C. The ingot was subjected to a homogenizing
heat treatment for 2 hours at 8000C followed by a room temperature water quenching. The
homogenized ingot was hot forged and then cold rolled, resulting in a final thickness of 0.3 mm.
Intermediate annealing at 5000C was required after every two or three passes. All test specimens cut
from the final plate were divided into two groups for various quenching procedures shown in Fig. 1.
These quenching procedures were selected in order to avoid any martensite stabilization problem,
since it was found that the aging of directly quenched alloys leads to the most rapid and serious
stabilization [13].

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188 Progress in Advanced Materials and Processes

Quenching in Up-quenching in an Quenching in

water at room oil bath at 105±50C for water at room
temperature 10 min temperature
UQ

Solution
treating at Quenching in an oil
SQOB Quenching in water at
8700C for bath at 105±50C,
room temperature
10 min for 10 min

Fig. 1. Schematic illustration of various quenching treatments

In order to study the effects of up-quenching and step-quenching processes on the aging
behavior and shape memory capacity of the alloy, specimens were carefully examined after aging at
200, 300 and 4000C for various time periods. The aging treatment was carried out in a salt bath
containing 60% KNO3 + 40% NaNO2. The martensitic transformation temperature (MS
temperature) was determined by measuring the variations in electric resistance with temperature.
The shape memory determinations were made by observing thin quenched and aged specimens
previously bent for about 30 deg before heating above the Af temperature. Tensile tests were
conducted at room temperature for samples aged at 4000C for various times. An optical microscope
and X-ray diffractometer were employed to examine the phases formed during aging.
To establish the amount of -phase that may occur in the alloy during aging, the study of the
microstructural morphology was undertaken. Quenched specimens were introduced into the 60%
KNO3 + 40% NaNO2 salt bath at fixed temperatures: 200, 250, 300, 350, 400, 450, 500 and 5500C.
The specimens were then annealed for times up to 2048 min, and quenched in water at room
temperature. Afterwards, the analysis of the formed phases was made by using optical microscopy
and X-ray diffraction spectroscopy.

3. RESULTS AND DISCUSSION

Optical microscopy observations of up-quenched and step-quenched specimens reveal the

parent-phase grain boundaries and the martensite structure, as shown in Fig. 2. From the X-ray
diffraction patterns of the specimens, the lattice parameters a, b, c, and were obtained and they
are listed in Table 1.
The alloy exhibits two ordering processes prior to martensitic transformation: bcc B2 and
B2 DO3. The presence of M18R type martensite in examined specimens confirms B2 DO3 order
transition.

UQ 50x SQOB 50x

Fig. 2. Optical micrographs of the microstructure of quenched specimens
 Materials Science Forum Vols. 453-454 189

The MS temperatures of quenched specimens, determined by measuring the variations in

electric resistance with temperature, are given in Table 1.

Table 1 Structure parameters of 18R martensite and Ms temperatures of up-quenched

and step-quenched specimens

Specimen Structure parameters of 18R martensite MS [0C]

a [nm] b [nm] c [nm] [deg] [deg]
UQ 0.4460 0.5320 3.8345 89.10 61.62 84
SQOB 0.4470 0.5305 3.8380 89.25 61.37 89

Quenched specimens of the alloy have shown shape memory recovery (SM recovery) in the
range 93-96%. The influence of various quenching procedures on SM recovery was not noticeable,
as reported previously for Cu-25.38Zn-3.3Al and Cu-18.05Zn-5.35Al alloys [14].
The aging of the alloy in the temperature range from 200 to 4000C caused a decrease in MS
temperature and SM recovery contrary to quenched specimens (Fig. 3). The aging times required at
each temperature to initiate the changes in the two properties conformed approximately to an
Arrhenius relationship (Fig. 4). The activation energies obtained from that relationship are
presented in Table 2.
UQ nad SQOB specimens UQ and SQOB specimens

100 100

90 80
SM recovery [%]
Ms temperature [C]

80 60
40
70
20
60
0
50
-20
40
1 2 3 4 5 6
0 1 2 3 4 5 6
log(time[sec])
log(time[sec])
UQ 200 SQOB 200 UQ 300 UQ 200 SQOB 200 UQ 300
SQOB 300 UQ 400 SQOB 400 SQOB 300 UQ 400 SQOB 400

a) b)
Fig. 3. Diagrams showing the influence of the aging time and temperature on the properties
of Cu-22.3Zn-5.1Al alloy: a) MS temperature; b) SM recovery
SQOB

-1.5
-2
-2.5
log[1/t50]

-3
-3.5 SMR
-4
Ms
-4.5
-5
-5.5
1.40E-03 1.60E-03 1.80E-03 2.00E-03 2.20E-03
1/T

Fig. 4. The Arrhenius plots of aging time vs. temperature to reach 50% decrease in MS
temperature and SM recovery
190 Progress in Advanced Materials and Processes

Table 2 Activation energies obtained from property measurements

Activation energy [kJmol-1]

Property
UQ SQOB
Decrease in MS temperature 62.8 60.9
Loss of shape memory capacity 73.2 72.8

Possible mechanisms causing a decrease in MS temperature of UQ and SQOB specimens are

the following:
• Change in chemical composition due to formation of solute-lean precipitates [2].
• Formation of segregates or precipitates, which interfere with either the nucleation or the growth
of the martensite [2].
• Large decrease in grain size [2].
• Change in degree or type of the order in the high temperature phase [2].
In this study, a large decrease in -grain size was not noticed. But, X-ray diffraction and
optical microscopy examinations indicate that the decrease in MS temperature during aging could be
caused by the formation of precipitates (Fig. 5). A plate-shaped product was observed in the
specimens aged at 3000C as shown in Fig. 5.a. The phase was identified as 1 bainite [9] with lattice
parameters: a=0.469 nm, b=0.264 nm and c=1.962 nm, which was ultimately transformed into the
fcc -phase. At 4000C, only a rod-shaped precipitate was formed. It was detected as fcc -phase
with the lattice parameter a=0.369 nm. In specimens aged at 2000C, formation of -precipitate was
observed. Furthermore, a change in DO3 order or a B2 DO3 transition [2] may occur.

500x 200x
Fig. 5. Optical micrographs of the microstructure of specimens aged for: (a) 150 min at 3000C; b)
60 min at 4000C.

The times required at each aging temperature to initiate a decrease in MS temperature were
comparable with the times required to initiate a change in SM recovery. The similarity between the
activation energies derived from the loss of SM recovery and from changes in MS temperature
indicates that similar rate controlling processes were operative for each property.
The activation energies derived from the measurements of shape memory can be used with
the Arrhenius equation to predict the life expectancy of shape memory devices operating at
temperatures lower than those examined. These predictions (Table 3) are based on the assumption
that the particular Arrhenius relationships are extrapolated for the lower temperature range. The
obtained values indicate that the memory devices made from UQ and SQOB specimens of Cu-
22.3Zn-5.1Al alloy will lose their shape memory properties after total exposure at 1000C for 68 and
71 days, respectively. But, UQ and SQOB specimens have a relatively long life expectancy at
temperatures below 500C.
 Materials Science Forum Vols. 453-454 191

In order to determine the amount of -phase that may occur in the alloy as a result of aging,
microstructural analysis was made, and a time-temperature-transformation (TTT) diagram drawn
(Fig. 6). The lattice parameter of the fcc -phase was a=0.369 nm.
Since most likely the formation of structures consisting of the -phase has led to the
decrease in Ms temperature and SM recovery, it is very important to establish the amount of -
phase, which would weaken the stability of the shape memory effect. In this study, it was found that
the specimens with more than 20 vol% of -phase had lost most of their shape memory. In
specimens aged at 2000C for 9.5 hours, SM recovery ranged from 64 to 70%. In their
microstructures about 10 vol% of -phase was observed. The aging for prolonged times caused the
increase in amount of -phase concomitant with degradation of shape memory capacity. So, after
aging at 2000C for 25 hours, SM recovery could not be recognized. Relatively high SM recovery
values were observed after aging at 3000C for 20 min, but aging for 55 min caused the loss of
memory behavior. Specimens aged at 4000C for 3 min, exhibited some SM recovery. However, the
prolonged aging resulted ultimately in the loss of SM capacity.

Table 3 Estimated life of Cu-22.3Zn-5.1Al shape memory alloy

Temperature [0C] UQ SQOB

150 4.2 days 4.5 days
100 68 days 71.3 days
80 259 days 270 days
50 7.2 years 7.4 years
25 70.7 years 71.8 years

The Arrhenius plot of annealing time vs. temperature to develop a microstructure with 20
vol% of -phase in total has been drawn. The activation energy of -precipitation in Cu-22.3Zn-
5.1Al alloy is thus determined to be 71±3 kJmol-1. This value is similar to the activation energy
value derived from the loss of SM recovery, suggesting that the precipitation of 20vol% -phase is
of dominant influence on the degradation of shape memory capacity.

600
20% 300 7
550
250 6
500
Yield stress [MPa]

Elongation [%]

5
Temperature [ C]

450 15% 30%

200 Rp0.2

400 4
150
350 3
300
10%
100 A
2
250 50
25%
1
200
0 0
150
0 1 3 10 20 30 40 50 60
0 1 2 3 4 5 6 7 8 9 10 11 12 13
ln(time[sec]) Time [min]

Fig. 6. Fig. 7.
Fig. 6. The TTT transformation diagram of -precipitation in Cu-22.3Zn-5.1Al alloy
Fig. 7. The variation in yield stress and tensile elongation during aging at 4000C
192 Progress in Advanced Materials and Processes

Very short life expectancy for the alloy at temperatures above 1500C was indicated by SM
determinations. Moreover, the tensile tests performed at room temperature showed a significant
reduction in yield stress and tensile elongation for specimens aged at 4000C (Fig. 7). So, it can be
concluded that the Cu-22.3Zn-5.1Al alloy is unsuitable for operation at relatively high temperatures
and long working conditions. But, the results shown in Table 3 indicate that the examined alloy is a
preferred material for commercial exploitation at temperatures below 500C.

4. CONCLUSIONS

1. During aging at temperatures from 200 to 4000C, martensite in Cu-22.3Zn-5.1Al alloy is

transformed to -phase concomitant with degradation of the shape memory capacity.
Specimens with more than 20 vol% of -phase were found to lose most of their SM
capacity.
2. MS temperature decreases during aging contrary to quenched specimens. The similarity
between the activation energies derived from the loss of SM recovery and from changes
in MS temperature indicates that similar rate controlling processes were operative for
each property.
3. The aging at 4000C resulted in significant reduction in yield stress and tensile
elongation.
4. UQ and SQOB specimens have a relatively long life expectancy at temperatures below
500C, suggesting that the alloy could be used for the construction of shape memory
devices operating at temperatures up to 500C.

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Progress in Advanced Materials and Processes
10.4028/www.scientific.net/MSF.453-454

Aging Effects in Cu-Zn-Al Shape Memory Alloy

10.4028/www.scientific.net/MSF.453-454.187

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