Materials Science and Engineering A 417 (2006) 225229

CuAlNiMn shape memory alloy processed by mechanical

alloying and powder metallurgy
Z. Li , Z.Y. Pan, N. Tang, Y.B. Jiang, N. Liu, M. Fang, F. Zheng
School of Materials Science and Engineering, Central South University, Room 410,
Changsha 410083, PR China
Received in revised form 22 October 2005; accepted 22 October 2005

Abstract
The CuAlNiMn shape memory alloy has been fabricated by mechanical alloying and vacuum hot pressing and hot extrusion. SEM and X-ray
diffraction analysis have been used to characterize the pre-alloyed powders and the hot extruded sample solution treated at 850 C for 10 min and
then water-quenched. The shape memory recovery of the quenched sample is measured to be 100% as it is recovered in boiling water for 40 s
after deformed to 4.0%, and the shape memory recovery of the sample remains 100% as it is subjected to deforming and recovering for 100 times
cycling.
2005 Elsevier B.V. All rights reserved.
Keywords: CuAlNiMn shape memory alloy; Powder metallurgy; Mechanical alloying

1. Introduction
There has been a major interest on Cu-based shape memory alloys (SMAs) mainly due to their low cost and relative ease of processing [13]. Among Cu-based shape memory alloys, CuAlNi alloy has higher thermal stability than
that of CuZnAl alloy [47]. Moreover, addition of Mn in
CuAlNi SMA has been reported enhancing the thermoelastic
and pseudoelastic properties [8]. So, the CuAlNiMn system
is selected in this study.
It is difficult to maintain the desired chemical compositions
and control the grain size of Cu-based SMAs by the conventional
casting method. In general, the composition change will shift the
transformation temperature and coarse grains will weaken the
mechanical properties of alloys.
It has been reported that mechanical alloying (MA) and powder metallurgy (P/M) with hot isostatic press (HIP) can be
used to fabricate Cu-based SMAs [912]. It is simpler to use
P/M to produce near-net shape alloy products and give better controllability of the composition and grain sizes. However,
the shape memory effect of the SMAs fabricated by the combining method of MA and the conventional P/M is declining

Corresponding author. Tel.: +86 731 8830264; fax: +86 731 8876692.
E-mail address: lizhou6931@163.com (Z. Li).

0921-5093/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2005.10.051

very fast with the cycling of deformation [9]. In this study, the
high-energy planetary ball milling is applied to convert the elemental powder mixtures of Cu, Al, Ni and Mn into pre-alloyed
powders. The pre-alloyed powders are compacted by vacuum
hot pressing and then hot extrusion to obtain the final alloy
sample.
The purpose of this work is to study the effect of MA on
the microstructure of the pre-alloyed mixture of powders and
the properties of the CuAlNiMn SMA prepared through ball
milling, plus vacuum hot pressing and hot extrusion.
2. Experimental procedures
2.1. Preparation of pre-alloyed powders
In the MA process, a QM-1F high-energy planetary ball mill
with four stainless steel vials was used. Each vial contained
hardened steel balls of different sizes (6, 10 and 20 mm in diameter). The ball-to-powder weight ratio (BPR) used was 15:1. The
specification of elemental powders and the initial mixture were
shown in Table 1.
The sealed vials were evacuated and then filled with argon to
avoid oxidation of the mixture. The mixture was then mechanical milled for 1, 5, 15, 25, 35 and 45 h at a speed of 300 rpm,
respectively.

Z. Li et al. / Materials Science and Engineering A 417 (2006) 225229

226

Table 1
Specification of elemental powders and mixture

Size (mesh)
Purity (%)
Composition of
mixture (wt.%)

Cu powder

Al powder

Ni powder

Mn powder

200
99.0
81

200
99.9
12

200
99.9
5

200
99.0
2

The structure of the hot-extruded sample solution-treated at

850 C for 10 min then water-quenched was investigated using
X-ray diffraction also.
2.5. SEM observation
The morphology and the elemental mapping images of the
hot-extruded sample solution-treated at 850 C for 10 min then
water-quenched was observed using scanning electron microscope (SEM) Sirion 200 equipped with EDAX GENESIS 60.

2.2. Vacuum hot pressing and hot extrusion

The vacuum hot pressing consisted of a 30 t hydraulic press
and a two-action piston die of 30 mm bore diameter. The prealloyed powders mechanical milled for 45 h were compacted
at 850 C in vacuum of 101 Pa under pressure of 30 MPa for
120 min. The green compact (a relative density over 94.8%) in
the evacuation of Cu-capsule was hot extruded at 900 C. The
extrusion ratio was 90:1.
2.3. Measurement of shape memory effect

3. Results and discussions

3.1. The structural evolution during MA
The structural evolution during MA of the Cu, Al, Ni and
Mn powder mixture is shown in Fig. 2. The pattern of 1 h MAed
powders is taken as the reference condition where the diffraction
peaks of initial components of Cu, Al, Ni and Mn appear. The

A strip specimen of 20 mm in length 2 mm in width

0.5 mm in thickness was cut off from the hot-extruded rod. The
strip was solution-treated at 850 C for 10 min and then to waterquenched. The phase transformation temperatures Ms , Mf , As
and Af were measured by the electrical resistance method to be
30, 15, 46 and 65 C, respectively. The quenched strip was bent
to 90 (see Fig. 1) at room temperature. The bent strip was put
into boiled water for 40 s and then the angle 1 was measured.
The maximum deformation strain, , was pre-determined as
4% for D = 12 mm. The recovery, , and the deformation strain,
, can be calculated as the follows:



90 1
=
100%
(1)
90
and
=

t
D+t


100%

(2)

Fig. 2. XRD patterns of powder after different milling time.

Where, t was the specimen thickness and D was the diameter

of curvature [9].
2.4. X-ray diffraction analysis
A small amount of milled powders was removed after certain
milling time (at 5, 15, 25, 35 and 45 h) from the container in an
argon glove box and investigated using X-ray diffraction (XRD)
with Cu K radiation in Dmax-2500 diffractometer.

Fig. 1. The arrangement of shape memory effect measurement.

Fig. 3. Changes of crystallite size and micro-strain of Cu as a function of milling

time.

Z. Li et al. / Materials Science and Engineering A 417 (2006) 225229

227

Fig. 4. Changes of peak positions and lattice parameters of Cu matrix as a

function of milling time.
Fig. 7. Change of the shape memory recovery, , as a function of deforming
cycling.

Fig. 5. The XRD pattern of sample hot-extruded and solution-treated at 850 C

for 10 min then water-quenched 1-122 M , 2-202M , 3-0018M , 2201 , 4-128 M 5208M , 6-1210M (2010M ) 7 1214M , (2014M ), 8-2221 , 9 2016M , 10-2020M
(1220M ), 11-4001 , 12-040M , 13-320M , 14 1226M , 15 3212M (4221 ).

intensities of diffraction peaks of Mn, Al and Ni are lower than

that of Cu diffraction peaks because of their small amount in
the overall composition. The height of all the diffraction peaks
decrease with balling time while the width of peaks increase. It
is caused by the decrease of crystallite size and the increase of
micro-strain due to a high stresses evolving during milling balls
impacts. Considering that the increase of peak widths mainly
consists of the Cauchy part that caused by decrease of crystallite size and Gauss part caused by increase of micro-strain, the
XRD profiles can be fitted by Pearson-VII function. Then the
average crystallite size D and micro-strain can be calculated
by substituting the fitted integral breadth into D = K/Cf cos
f cot , where f is Cauchy integral breadth
and = (1/4)G
C
f
and G is Gauss integral breadth, the constants K is 0.9 and is
0.15405 nm. The changes in crystallite size and micro-strain of
Cu matrix as a function of milling time are shown in Fig. 3. The
crystallite size decreases while the micro-strain increases with
balling time.

Fig. 6. TEM images of the martensite structure of quenched sample (a) BF image and (b) corresponding diffraction pattern with zone axis of [010].

228

Z. Li et al. / Materials Science and Engineering A 417 (2006) 225229

The intensity of the Ni diffraction peaks and most of Al and

Mn diffraction peaks become indistinguishable after MA 15 h. A
slight shift of position of Cu diffraction peaks (see Fig. 4) reflects
the diffusion of Al, Ni and Mn into Cu matrix. The position of
Cu diffraction peaks moved towards low-angle indicates that the
lattice parameters of Cu matrix increase with milling time.
Plastic deformation and interdiffusion of elements control
the formation of amorphous and crystal phase [13], the mixing
of elements is accelerated by diffusion of Al, Ni and Mn along
dislocations and grain boundaries of Cu solid solution. After
35 h MA, only the diffraction peaks of a single phase with fcc
structure appear (see Fig. 2). The X-ray diffraction results, which
agree well with the observation of Kaneyoshi et al. [14], lead to

the conclusion that a single phase solid solution is formed after

35 h MA of the elemental power mixtures. Increasing the milling
time to 45 h, the XRD pattern where the spectrum is consisting of
Cu diffraction peaks superimposed on top of broad background
presents. This broad background is associated with amorphous
phase [15].
3.2. The structure of quenched sample
The XRD pattern of the hot-extruded sample solution-treated
at 850 C for 10 min then water-quenched is given in Fig. 5.
The characteristic diffraction peaks of martensite structure, as
suggested by Saburi and Wanyman [16] and Kubo and Shimizu

Fig. 8. SEM microstructures and elemental mapping images taken from the (b) of hot-extruded sample and solution-treated at 850 C for 10 min then
water-quenched.

Z. Li et al. / Materials Science and Engineering A 417 (2006) 225229

[17] for 18R, can be found existing between two theta of 3585 .
The 1 phase can be found existing also.
The microstructure and electron diffraction pattern of the
martensite above are showed in Fig. 6. The information of
the martensite structure can be obtained from the photos. (1)
Sub-structure of the martensite is the basal-stacking fault (see
Fig. 6a). (2) The distance between the two strong reflection spots
(the reciprocal unit interlayer spacing (RUIS)) has been divided
into three parts by two weak reflection spots and can be characterized with a structure of long period stacking order (LPSO).
This characteristic structure is similar to that of M18R martensite found in Cu30 Au25 Zn45 [17].
3.3. Shape memory effect (SME) of quenched sample
The shape memory effect of the strip cut off from the hotextruded sample solution-treated at 850 C for 10 min then
water-quenched is measured with the results showed in Fig. 7.
The sample is undergone 4.0% deformation and then recovered
in boiling water for 40 s. The shape memory recovery, , is measured to be 100%. The of the sample has remained 100%
as it is subjecting to deformation and recovering for 100 times
cycling. This is much higher than that of the MAed CuAlNi
shape memory alloy [9]. The reported initial recovery of the
CuAlNi shape memory alloy was 68% [9] and dropped to
30% in the second test where the deformation strain used was
only 1%. The internal cracks and the stress concentration around
pores caused a rapid degradation of the SME in MAed CuAlNi
shape memory alloys [9].
The scanning electron microscopy and elemental mapping
images of the hot extruded sample solution-treated at 850 C for
10 min then water-quenched are presented in Fig. 8. It is worth
to point out that the metallurgical bonding among the matrix
particles has replaced the mechanical bonding or engagement
(see Fig. 8a and b). Furthermore, the internal cracks and pores
are not found in the photos. We can draw a conclusion that the
employment of vacuum hot pressing and hot extrusion here does
help eliminating the existence of pores and promoting metallurgical bonding among the particles of Cu matrix. The average
grain size of solution-treated sample is about 3 m, where a
small part of grains have merged together and grown up. There
is self-accommodation configuration of martensite inside some
of those merged grains (see Fig. 8a and b).
The elemental mapping images taken from the Fig. 8b
present in Fig. 8ce (the size of elemental mapping image is
the same as that of Fig. 8b) allow to conclude that the distribution of the chemical composition is homogeneous. The
average composition determined by energy dispersive spectroscopy is 81.6 wt.% Cu, 11.8 wt.% Al, and 4.9 wt.% Ni and
1.7 wt.% Mn.

229

4. Conclusions
(1) MA can be successfully applied to prepare Cu, Al, Ni and
Mn pre-alloyed powders. A single phase of fcc structure
with lattice parameter close to that of Cu is produced after
MA for 35 h.
(2) Metallurgical bonding among the particles in Cu matrix has
been found to replace the mechanical bonding or engagement after hot extruded at 900 C with the extrusion ratio of
90:1.
(3) Crack- and pore-free and homogeneous samples can be produced through vacuum hot pressing and hot-extrusion.
(4) The shape memory recovery of the hot-extruded sample
solution-treated at 850 C for 10 min then water-quenched
is measured to be 100% as it is recovered in boiling water
bath for 40 s after deformed to 4.0%, and the shape memory
recovery of the sample remains 100% as it was subjected to
deforming and recovering for 100 times cycling.
Acknowledgements
This study was supported by the Postdoctoral Science Foundation of China (2004036427) and Ph.D. Programs Foundation
of ministry of education of China (20040533069).
References
[1] R. Kainuma, S. Takahashi, K. Ishida, Metall. Mater. Trans. A 27A (1996)
2187.
[2] Z. Li, M.P. Wang, Trans. Nfsoc. 12 (1) (2002) 6.
[3] G. Zak, A.C. Kneissl, G. Zatulskij, Scripta Mater. 34 (3) (1996) 363.
[4] V. Recarte, I. Hurtado, J. Herreros, M.L. No, J. San Juan, Scripta Mater.
34 (1996) 255.
[5] V. Recarte, R.B. Perez-Saez, M.L. No, J. San Juan, J. Phys. IV 7 (1997)
329.
[6] T. Daricek, J. Lasek, N. Zarubova, J. Phys. IV 11 (PR8) (2001) 179.
[7] V. Recarte, J.I. Perez-Landazabal, A. Ibarra, Mater. Sci. Eng. A 378
(2004) 238.
[8] M.A. Morris, T. Lipe, Acta Metall. 42 (1994) 1583.
[9] S.M. Tang, C.Y. Chhung, W.G. Liu, J. Mater. Process. Technol. 63
(1997) 307.
[10] A. Ibarra, P.P. Rodriguez, V. Recarte, Mater. Sci. Eng. A 370 (2004)
492.
[11] R.B. Perez-Saez, V. Recarte, O.A. Ruano, M.L. No, J. San Juan, Adv.
Eng. Mater. 2 (2000) 49.
[12] J. San Juan, R.B. Perez-Saez, V. Recarte, M.L. No, G. Caruana, M.
Lieblich, O. Ruano, J. Phys. IV 5 (1995) 919.
[13] R.B. Schwarz, R.R. Petrich, C.K. Saw, J. Non-Cryst. Solids 76 (1985)
281.
[14] T. Kaneyoshi, T. Takahashi, Y. Hayashi, J. Jpn. Inst. Met. 56 (1992)
517.
[15] H. Huang, P.G. McCormic, J. Alloys Compd. 256 (1997) 258.
[16] T. Saburi, C.M. Wanyman, Acta Metall. 27 (1979) 979.
[17] H. Kubo, K. Shimizu, Martensite Trans. JIM 17 (1976) 330.