Journal of Manufacturing Engineering, September, 2013, Vol. 8, Issue.

3, pp 188-191

EFFECT OF ALLOYING ON MICROSTRUCTURE AND SHAPE

MEMORY CHARACTERISTICS OF CU-ZN-NI SHAPE
MEMORY ALLOYS
*
Sathish S1, Mallik U S 2 and Raju T N3
1
Department of Mechanical Engineering, Dr.Ambedkar Institute of Technology, Bangalore - 560 056, India
2
Department of Mechanical Engineering, Siddaganga Institute of Technology, Tumkur -572103,India

ABSTRACT
Ni-Ti and Cu–based shape memory alloys, such as Cu-Zn-Al and Cu-Al-Ni, are presently
available for commercial use in shape memory applications. Ni-Ti shape memory alloys exhibit better
shape memory properties and good corrosion resistance than Cu-based shape memory alloys (SMAs).
However Ni-Ti in finished form is very expensive because of fabrication difficulties associated with
melting and forming. In many applications, Cu-based shape memory alloys provide a more
economical alternative to Ni-Ti shape memory alloys in terms of melting and designing into desired
form. Cu-Zn-Ni shape memory alloys in the range of 38- 55 wt. % of Zinc and 0- 15 wt % of nickel,
exhibit β- phase at high temperature, the alloys upon quenching high temperature to lower
temperatures undergoes a martensite transformation manifesting shape memory effect. In the present
study Cu-Zn-Ni alloys in the above said range are prepared through ingot metallurgy route on argon
atmosphere. The characterization of the alloys revealed the formation martensite phase exhibited good
ductility and shape memory effect. The results are given and discussed in detail.

Key words: Cu–Zn–Ni shape Memory Alloy and Transformation Temperature and Shape Memory
Effect.

1. Introduction
Among the many alloy systems exhibiting have been explored for their potential use. Currently Cu-
shape memory effect (SME), Cu-Al-Ni and Cu-Zn-Al Zn-Al and Cu-Al-Ni [5] shape memory alloys are
shape memory alloys (SMAs) have been studied commercially available and put to use in many practical
extensively over the years [1]. Most of the copper-based applications. The alloys are suitably modified to meet
shape memory alloys are easy to produce, process and specific requirements for practical use by selectively
are also less expensive when compared to Ni-Ti shape alloying with suitable quaternary and grain refining
memory alloys. However, Cu-Al-Ni and Cu-Zn-Al additions. Accordingly Cu-Zn-Al-Ni, Cu-Zn-Al-Ni-Mn
shape memory alloys in the polycrystalline state are and Cu-Zn-Ni-Ti-Mn etc [6] are developed and put use
brittle and therefore, be easily worked due to the high in many commercial applications. Alloys also grain
degree of order and high elastic anisotropy of the parent refines such as B, Co, Fe, Ti, V and Zr to improve
β-phase (austenitic) [2]. mechanical properties.
Current Cu-based shape memory alloys [3] are
derived from three binary alloy systems, Cu-Zn, Cu-Al 2. Experimental Procedure
and Cu-Sn. Among these martensitic transformation in
Cu-Sn alloys are not ideally thermo elastic and suffers 2.1. Alloy preparation and composition analysis
from a rapid degradation of a shape memory properties Pure copper, Zinc and nickel were taken in
during ageing even at moderate temperature and it is right quantities from figure 1 phase diagrams to weigh
also very brittle and composition range is less. These 500 g of the alloy in total and were melted together in
alloys are therefore of theoretical interest than as an induction furnace under an argon atmosphere. The
potential commercial shape memory alloys. molten alloy was poured into a cast iron mould of
Cu-Zn based alloys containing Al, Si, Sn, Ga, dimensions 150 mm x 100 mm x 3 mm and allowed to
or Mn as ternary alloy and Cu-Al-base ternary alloys solidify. The ingots were then homogenized at 1073K in
with alloying elements such as Ni, Be, Zn and Mn [4] β-phase for 6hrs under an argon atmosphere. The
chemical compositions of the cast alloys were
*Corresponding Author - E- mail: [email protected]
The content of this manuscript has been presented in 3rd International Conference on Recent Advances in Material Processing Technology (RAMPT’13)

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 Journal of Manufacturing Engineering, September, 2013, Vol. 8, Issue. 3, pp 188-191

determined using a Perkin-Elmer integrally coupled The transformation temperatures were determined using
plasma-optical emission spectrophotometer. a differential scanning calorimeter (DSC) by adopting a
heating and cooling rate of 10oC/min. The
2.2 Thermomechanical treatments and polycrystalline samples were analyzed by X-ray
characterization diffractometer identify the phases present in them at
The homogenized alloy samples were hot room temperature. The strain recovery by SME of the
rolled at 1073K to a thickness of 1 mm. The hot rolled alloys was determined by carrying out bend tests on 1
samples were betatized for 30 min at 1073K and step mm thick specimens and measuring the initial and final
quenched into a boiling water bath (~373K), followed bend angles just before heating, i.e. in the martensitic
by quenching them into a water bath at room phase, and immediately after heating, i.e. in the
temperature (~303K). Step quenching was used to avoid austenitic phase of the alloys. Optical microscopes were
the quench cracks and the pinning of martensitic plates used to study the microstructure, especially the
by excess dislocations retained on quenching from high morphology of the martensite formed. For optical
temperature [7]. The microstructure and morphology of microscopic studies the specimens were cold mounted
martensites formed were studied using an optical using resin and were prepared by fine polishing
microscope. following the standard metallographic practice polished
specimens were then etched using the etchant
K2Cr2O7(2 g-K2Cr2O7, 8 ml-H2SO4, 4 drops-HCl and
100 ml Water). The etched samples were thoroughly
cleaned with acetone and the microstructural
examination was carried out using optical microscopes.

3. Results and Discussion

3.1 Chemical composition, Transformation
temperatures of Ternary Cu-Zn-Ni SMAs
The chemical compositions of all the alloys
that were determined using an Inductively Coupled
Plasma-Optical Emission Spectrophotometer as shown
in table 1 and the corresponding Transformation
temperatures on heating and cooling were determined
by DSC analysis of the alloy samples. DSC for step-
quenched Alloy Cu–47.22 wt.% Zn–5.71 wt.% Ni alloy.
Transformation temperatures (K) above sample are
Austenite start 315K and Austenite finish 333K and
Martensite start 243K and Martensite finish 253K.
During heating the endothermic reaction marks the
transformation of martensite to austenite and during
cooling an exothermic reaction marks the reverse
transformation of austenite to martensite. In this alloy
system it can be observed that the temperature Mf,
below which the alloy will be completely martensitic,
varies from 223K to above 283K. Therefore these alloys
can be suitably designed for use in different temperature
and also for low temperature applications.

3.2 Shape memory effect (SME)

The shape memory effect in sheet specimens of
1 mm thickness was determined by bend test as shown
in figure 2. The flat sheet specimens of the alloys were
bent to a U-shape in the martensitic phase of the alloys
at T< Martensite finish (Mf). The alloys were then
Fig. 1 (a) Isothermal section of Cu-Zn-Ni at 1048K heated to above their Austenite finish (Af) temperature.
and (b) Liquidous projections The corresponding angles of bend before heating and

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 Journal of Manufacturing Engineering, September, 2013, Vol. 8, Issue. 3, pp 188-191

after heating to above Af temperature were measured 3.3 Phase and microstructural analysis
and the percentage of strain recovery was determined. Figure 3a shows the optical micrograph
These alloy systems exhibit significant strain recovery showing parent austenitic phase of the Cu–Zn-Ni alloy
by SME to the extent of 99% as shown in table 1.The samples.
amount of shape memory depends mainly on the
amount of martensite present in the alloy and the extent
of transformation of martensite to austenite. Mechanical
Properties of Cu-Zn-Ni SMAs The alloys exhibit good
hardness of over 189 VHN. The hardness of the alloys
shown in the austenitic phase at room temperature are
higher than in the martensitic phase at room temperature
(~30oC).
SME = θm / 180-θe Where θe = angle recovered on
unloading, d = 50mm, Strain (σ) = 2%, and θm = angle
recovered on heating

Fig. 2 Schematic diagram of the bend test to Figure.3 Microstructure of alloy Composition:
determine strain recovery by SME (a) optical micrograph showing parent austenitic
phase; (b) optical micrograph showing lath type
Table 1. Chemical composition of Cu-Zn-Ni SMAs martensite structure obtained on step quenching
and shape memory effect (SME)
The complete transformation of the parent
Alloy Chemical composition Strain austenitic phase to martensite can be observed in the
ID (wt.%) recovery by micrographs of the alloys whose transformation
Cu Zn Ni SME in temperatures lie around room temperature (~303K).
percentage Complete lath type martensitic structures with thin
1 48.22 45.00 6.65 66 martensitic plates or variants are formed in these alloys
2 44.15 50.35 5.66 68 as shown in figure 3b.
The different martensitic phases formed in the
3 50.78 43.40 5.98 76 polycrystalline samples of the step quenched alloys
4 48.96 48.04 2.96 60 were analyzed using X-ray diffractometers with Cu-Kα
radiation, at room temperature. X-ray diffraction was
5 39.14 51.09 9.61 72 also used to determine the phase and the contents of the
6 49.27 45.91 4.47 65 specimens which homogenized at 1073K and also the
sample which homogenized for 4 h. Figure 4a and 4b
7 44.49 44.93 3.05 99 shows that X-ray diffraction patterns for both heat
8 46.17 47.22 5.71 68 treated and compressively deformed specimens which
exhibit peaks. In the case of compressively deformed
9 48.50 45.59 5.82 88 specimens, peaks indicate that martensite phases
generated in the specimens were also observed.
10 45.24 51.66 3.05 92
11 48.34 48.34 7.99 78

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 Journal of Manufacturing Engineering, September, 2013, Vol. 8, Issue. 3, pp 188-191

β1' martensitic phase is predominant in the

(111)

40000
composition range of the alloys chosen. Two
kinds of martensites are observed in these
30000 alloys, i.e. β 1' (18R) martensite and γ1' (2H)
martensite with high density of twins.
Intensity ( Arb Units )

20000 (311)
ii. The transformation temperatures are highly
(202)
(0 0 1)

sensitive to the variation in zinc concentrations

(222)

(220)

of the alloy
(310)

10000
(222)
(211)
(200)

(110)
(210)

iii. The alloys exhibit good strain recovery by

SME. A strain recovery of up to 99% by SME
0
was observed in these alloys.
iv. The alloys exhibit good hardness of over 189
-10000 VHN.
40 60 80
2
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