JournaJoC

Materials
Processing
Technology
ELSEVIER Journal of Materials Processing Technology 63 (1997) 307-312

Preparation of Cu-AI-Ni-based Shape Memory Alloys by

Mechanical Alloying and Powder Metallurgy Method

S.M.Tang, C.Y. Chung and WG. Liu*

Department of Physics and Materials Science, City University of Hong Kong, Hong Kong.
*Department of Mechanical & Materials Engineering, The University of Western Australia, Australia.

Abstract

The conventional cast shape memory alloys (SMA) billets can be hot worked into components with unifornl cross sections. However,
near-net shape components can be made more easily by the powder metallurgy method which can save a lot of hot working procedures and
thus simplify the fabrication process. The elemental powders are pre-alloyed by high energy ball milling, this mechanical alloying process
significantly modifying the characteristics of the powders and shortening the sintering time. SEM, X-ray Diffraction analysis and DSC
thermal analysis have been used to characterize the pre-alloyed powders, the green compacts and the solution-treated compacts. After
suitable heat treatment, the shape memory property is produced. However, it is found that when the ball milling time is too long, the
amount of martensite produced by solid solution treatment and subsequent quenching will be lowered, and reflected in the endothernlic peak
during phase transformation in DSC analysis. This investigation is focused on the necessary conditions for fabricating Cu-AI-Ni-
based(CAN) shape memory ally by means of powder metallurgy.

Keywords: Cu-AI-Ni-based shape memory alloy, powder metallurgy, mechanical alloying

1. Introduction
hardened steel balls of 20mm and 10mm diameter. The ball-to-
In recent years, Cu-based shape memory alloys(SMA) have powder weight ratio(BPR) is 5: 1. The specification of elemental
been widely developed because of their more competitive cost and powders and the initial powder mixture is shown in Table 1.
easier fabrication process than for Ni-Ti SMA. Amongst Cu- The sealed vials were evacuated and then filled with argon gas
based SMAs, the CAN system has better thermal stability [1], this to avoid oxidation of the powders. The powder mixtures were
system therefore being selected in the present study. For the mechanical milled for Ihr, 5hrs, lOhrs, 15hrs, 20hrs and 40hrs at
preparation of SMAs, the conventional casting method has a speed of 100rpm.
difficulties in controlling the grain size. Coarse grains will
weaken the mechanical properties of alloys. It has been reported
that mechanical alloying(MA) and powder metallurgy(P/M) with Cu powder Nipowder
hot isostatic press(HIP) can be used to fabricate Cu-based Size(mesh) 200 200 200
SMAs[2-6j. PIM can reduce the hot working processes in Purity(%) 99 99.9 99.99
fabricating the near-net shape products and usually give better Composition of 82 14 4
control of grain size. MA produces pre-alloyed powders w'hich mixture(wt%)
can shorten the sintering time. However, no published work has
been done on the preparation of CAN SMA by MA and the 2.2 Cold compaction and sintering
conventional PIM with cold compaction. In this study, high
energy planetary ball milling was applied to convert the Cu-Al-Ni The compaction process consisted of a 40ton hand-operated
elemental powder mixture to pre-alloyed powders. Conventional hydraulic press and a single-acting piston die of 20mm bore
PIM with cold compaction was used to produce bulk Cu-AI-Ni- diameter. The pre-alloyed powders were compacted at a pressure
based SMA from the pre-alloyed powders by MA. The purpose of 900MPa in the die to form disc-shaped green compacts. The
of this study is to reveal the effect of MA on the microstructure sintering procedure of green compacts was perfonned in a tube
and properties of Cu-Al-Ni SMAs produced by general milling, furnace at 950°C for 20hrs under a protective Argon gas
pressing and furnace equipment in a materials laboratory. atmosphere, followed by furnace cooling. The sintered compacts
were solution-treated at 900°C for one hour followed by
quenching in room temperature water.
2. Experimental Procedures

2.1 Preparation ofpre-alloyedpowders 2.3 Methods ofcharacterization

In the MA process, a QM-IF high energy planetary ball mill a) particle size distribution: sieving method ASTM Ell;
with four stainless steel vials was used, each vial containing b) density measurement : ASTM designation 311-93;

0924-0136/97/$15.00 © 1997 Elsevier Science SA All rights reserved

PII S0924-0136(%)02641-6
308 SM. Tang et al. .IJournal of Materials Processing Technology 63 (1997) 307-312

c) microhardness testing : Matsuzawa MXT-CX7 tester,

polished specimen, 200gf and the
average of eight readings;
d) X-ray Diffraction : Siemens D500 X-ray diffractometer
(XRD) using CuKa. radiation;
e) optical microscopy : specimen was etched in FeCh
solution after the surface had been t
polished;
f) scanning electron : JEOL JSM-820 with energy
(SEM) dispersive microscope
spectroscopy (EDS); Fig. 1 The arrangement for the measurement of SME.
g) differential scanning : Perkin-Elmer DSC-7 at heating rate
calorimetry (DSC) of 20°C;
h) porosity measurement : Quantachrome AUTOSCAN 33
mercury porosimeter. 3. Experimental Results

2.4 Measurement o/shape memory effect(SME)[7] 3.1 X-ray diffraction analysis

A strip specimen 18mmlengthx2.5mmwidthxO.7mmthickness
was cut from the disc compact. The strip was then filed to a
thickness of 0.05mm. The thin strip was bent to 90°, as Fig.l,
and submerged into ice water for 1 minute. After unloading, it
spring-back to 82. The bent strip was put into boiling water for
half a minute and then angle 01 was measured. The maximum
deformation strain, e, was pre-determined as I % for d=5mm.
The recovery, R, and the deformation strain, e, can be calculated
as:
(1)
e = t/(d+t) x 100% (2)
In Fig.2, the structural evolution during MA of the Cu-AI-Ni
powder mixture was observed. The pattern of the Ihr MA curve
was regarded as a reference condition where the peaks of starting
components Cu, AI, Ni appeared. The peaks of the Al and the
Ni were lower than the Cu peaks because of their small amount in
the overall composition. As the MA time increased, the intensity
of all the diffraction peaks was decreased and became broader.
After MA for 15hrs, the intensities of the Ni peak and most of the
AI peaks became almost indistinguishable. A slight shift in the
position of the Cu peak reflected that the diffusion process of the
Al and Ni in the Cu matrix[Cu(AI, Ni)]ss was present. After MA
for 40hrs, the shift of the Cu peak was more significant and only
the peaks of a single phase with fcc structure appeared. The
lattice paranleters of these phases were found to be close to that
of the Cu element. The X-ray results, which agree well with the
observation by Kaneyoshi et al.[8], lead to the conclusion that a

Cu

Cu

Cu
AI
'AI

J\ IOhr

. J"'--. -~---~

..-.~ --J'\~~.~

:------------, (~~.) ,,~~

(3~
40hr'

S5 65 7(~ 7S eo
20

Fig.2 )CRD patterns of milled powder mixtures.

 S.M. Tang et al. / Journal of Materials Processing Technology 63 (1997) 307-312 309

.29

Fig.3 XRD patterns of solution treated'& quenched compacts.

single phase solid solution was fonned after 40hr MA of the lamellae became more refmed and disappeared progressively with
elemental powder mixtures. longer milling times as shown in Fig.4(c). Finally, pre-alloyed
Fig.3 illustrates the changes in the XRD patterns of CAN powders of a single phase solid solution were fonned through the
quenched compacts fabricated from powder mixtures milled for solid-state diffusion process. That was conftnned by the XRD
various times. An interesting observation is the peaks laid analysis in section 3.1. The particle size distribution for different
between 2e = 30° to 50° that represented martensite structures milling times is shown in Fig.6. With longer milling times,
(18R and 2H) fonned. The profile of the XRD curves was very coarser powder particles and thicker welded layer on the balls and
close to that of melted CAN SMA observed by Zhang et al.[9]. inner wall of vials were observed, indicating that even after MA
As the milling times increased, more martensite peaks appeared, for 40hrs, the milling process was still in the period of welding
but some of them were too weak to be distinguished. Further predominance under the milling parameters used in this study.
analytical works is needed to identify the different types of The grain size of conventionally cast Cu-based SMAs ranged
martensite structure. from Imm to 3mm in diameter[7] . In this study, the grain size
of sintered compacts decreased as the milling time increased.
3.2 Observation ofmilledpowders and compacts The mean diameter of grains for Ihr milled specimen was 2J.Ull.
For 40hr milled specimen, the mean grain diameter was smaller
The mechanisms of MA process include defonnation, fracture than O.SJ.Ull.
and cold-welding of the powder particles with a solid-state
diffusion[10-14]. The evolution of MA for the Cu-AI-Ni
elemental powder mixtures was observed through the SEM
metallography of the green compacts in the following stages.
a) Defonnation and welding between powder particles.
Fig.4(a) shows the typical morphology of a ductile system at the
beginning of MA (lhr). The dark areas were the defonned Al
particles embedded into Cu particles in bright areas. Since the Ni
content was too low, its particles were hard to identify.
b) Fonnation of lamellar structure. As the powder components
consisted of ductile phases, the continuous defonnation and
welding of particles leading to the lamellar microstructure as
shown in Fig.4(b). By EDS analysis, the Al content in the
lamellar structure was greater than 85%wt after Shr MA and
70%wt after 10hr MA. On the other hand, a layer of powder
beads stuck on the surface of balls and inner walls of vials were
observed after 15hr MA.
c) Defonnation of lamellar structure. As the lamellae was
further plastically defonned, it became brittle. The brittle
particles can easily fracture into smaller pieces. Therefore, these 4(a)
310 s.M. Tang et al.!Journal of Materials Processing Technology 63 (1997) 307-312

Figj shows the morphology of martensite found in the

quenched compacts which was similar to a typical thermal-elastic
martensite in the conventional melted CAN SMA.

3.3 Effect o./MA on microhardness, porosity and density

For the green compacts, the microhardness increased as the MA

time increased, as sho\\TI in Fig.7, this being the result of work
hardening as well as the increase in the amount of defects in the
milled powders. It was reported by Liu[l5] that the Al particles
in the green compacts which became liquid phase at the sintering
temperature, diffused into the Cu matrix during the sintering
process and then left pores inside the sintered compacts, which
explains the change of open pore porosity measured in this study.
For 5hr MA, the welding predominant milling produced coarse Al
particles that increased the porosity of the sintered compacts.
4(b) However, further milling fractured the Al particles into small

4(c)
Fig.4 Typical structures of green compacts fabricated from Fig.S Typical morphology of martensite structures observed
powders milled for: (a) Ihr; (b) lOhrs; (c) 40hrs. in solution-treated & quenched compacts.

Uii" )-'1 <53}lm

~ 53 to 125pm
70 c:::=:J 1251lm to 355}lm
(22ZZ2j 3551lm to 500pm
60 &SSSSI >500pm

~ 50
!c:: 40
.8
~
='
30
t:1
5
20
/
/

10

0
lhr 5hr IOhr IShr 20hr 40hr
Milling time (hr)
. Fig.6 Particle size distribution ofmiIled powders.
 SM. Tang et a1. / Journal of Materials Processing Technology 63 (1997) 307-312 311

350 440
\0
• r-_-

--------
420 . microhardness
300
400
\/ " "- "- open pore porosily 9

>
\! ~
f 250 C d\ 7 .~
~
u
380 \\.~
E
u 6 c
" 360

\
~
0-
200 \ ~
5
J:. -=;:
J:.
340 \ c
Co
I:u u \ 4 ~
i 150 i 320 -
\ 0-
\ <J ___
C
I-

100 300 2
---..,:,
280
50 0 10 20 30 40
0 10 20 30 40
Milling Time(hr) Milling Time(hr)

Fig.7 Milling time vs microhardness of green compacts. Fig.8 Milling time vs microhardness & open pore
porosity of sintered compacts.

6.6 ,..,-----,------;------r----~
6.5
f
,...."\ 180 - 180

~:
sinlered density
6.5
/ \\ -~- enthalpy 6.0 :§ A,
0 160 . M, 160
6.4 >.

~///
~"
i 6.3
- 5.5 ~
J:.
E
u G
~
140 140
G
~
.~ 5.0 "
,
c
6.2
. < 120 120 i
a" ',-- .~. 4.5
~
6.1
'--- ~ 100 //
100
?:"'"
,/.-0/
./
6.0 4.0 /e-
./

80 / 80
/
if'
5.9 •
'--:0:----1-'-0----2'-0----3-'-0------'....J 3.5 60 60
40 10 15 20 25 30 35 40
Milling Time(hr) Milling Time(hr)

Fig.9 Milling time vs sintered density & transformation Fig. 10 Milling time vs As and M s
enthalpy.

pieces that reduced both the porosity and the mean pore diameter alloying of powder mixtures was obviously not adequate to
in the sintered compacts. In Fig.8, the effect of open pore provide homogeneous composition for SMA until MA for 10hrs.
porosity on the microhardness of sintered compacts is shov.n, Well-alloyed powders milled for 15hrs gave the highest value of
greater porosity reducing the microhardness of the specimen. enthalpy. Then, the transformation enthalpy dropped with longer
Other factors such as a smaller particle size and a greater MA times. Higher density of compacts will give better
hardness of particles will lead to a reduction in the density of the mechanical properties and also provide more reversible
compacts. With the longer milling times, these two factors martensites. The variation in the value of the enthalpy as a
caused a variation in the sintered density, but the latter factor function of the MA time has been observed in Fig.9 to coincide
seems to be dominant after MA for 15hrs,as shown in Fig.9. with the change in the density of the compacts.

3.4 Differential scanning calorimetry analysis

In DSC analysis, the values of Ms and the transformation
enthalpy for different milling times are more interesting for
discussion. The change ofMs is shown in Fig.lO. Kaneoshi et
al.[8] have reported that the increase in grain refinement with
longer milling times might enhance the constraints amongst grains
that suppresses the martensitic transformation. Therefore, both
the Ms and As increased as the MA time increased.
The variation of the transformation enthalpy of the quenched
compacts with milling times is shown in Fig.9. No phase
transformation was detected in the Ihr and 5hr milled specimens.
If the XRD results below 5hr milling are referred to, the degree of
3.5 Testing ofSME
From section 3.4, the 15hr milled pre-alloyed powders provided
the highest value of phase transformation enthalpy, so that their
quenched compact was selected for the SME test. A strip cut
from this compact was tested. The recovery, R, was measured to
be 68% at the first time, but dropped to 30% in the second test.
Internal cracks and stress concentration around the pores may
cause rapid degradation in the SME. The defect may be
minimized by use of the P/M method with HIP, which can secure
homogeneous products with a higher density and a smaller
porosity.
312 SM. Tang eta!'!Journal of Materials Processing Technology 63 (1997) 307-312
4 Conclusion
I) MA can be applied to prepare Cu-AI-Ni-based pre-alloyed
powders. A single phase of fcc structure with lattice parameter
close to that of Cu was produced after MA for 40hr of the
elemental powder mixtures;
2) The grain size of sintered compacts are refined with longer
milling times, and are smaller than 2~lm;
3) The microhardness of green and sintered compacats increase
with longer MA times, but the microhardness of sintered
compacts decreases with greater open pore porosity;
4) The density of the compacts is affected by the hardness and the
size of the powder particles. The highest density of green and
sintered compacts were obtained from the powder mixtures with
MA for 15hr;
5) Conventional P/M with cold-compaction can be used to
produce Cu-AI-Ni-based SMA with pre-alloyed powders by
MA. The highest phase transformation enthalpy, 6.36J/g, was
measured from the quenched compact made of 15hr milled
powder mixtures. The best recovery in the SME test was found
to be 68% for the quenched compact of 15hr milled specimen
tmder a maximum deformation strain of 1%.
Reference
[I] K. Sugimoto, K. Kamei and M. Nakaniwa;'Engineering
Aspects of Shape Memory Alloys', Eds. T.W. Duerig,
London, Butterworth-Heineman Ltd., (1990) 89-95.
[2] R.D. Jean, TY. Wu and S.S. Leu; Scripta Metall., 25(1991)
883-888.
[3] M. Igharo, and lY. Wood; Powder Met., 28(1985)
131-139.
[4] J.Janssen, F. Willems, B.Verelst, l Maertens, and L.Delaey;
l de Physique, 43(1982) C4-809·812.
[5] N. Nakanishi, T. Shigematsu, and N. Machida: in Proc.
Conf. 'International Conference on Martensitic
Transformations', Monterey, CA, July 1992, Monterey Inst.
for Advanced Studies, ppI077-1082.
[6] YD. Kim and C.M. Wayman; Scripta Metall., 24(1990)
245-250.
[7] W.Z. Li and lP. Zhou, South China University of
Technology (510641).
[8] I. Kaneyoshi, T. Takahashi, Y Hayashi, and M. Motoyama;
l Japan Inst. Mets., 56(1992) 517-623 (in Japanese).
[9] YM. Zhang, IN. Gui, R.H. Wang, L.M. Gao, YG. Wu and
YL. Tang; l Phys. Condens. Matter, 5(1993), 2719-2728.
[10] F. Thummler and R. Oberacker; 'An Introduction to
Powder Metallurgy, I. Jenkins and lV. Wood (Eds.), The
The Inst. of Materials, The University Press, Cambridge,
(1993) pp. 181-261.
[11] F.V. Lenel;'Powder Metallurgy- Principles and
Applications', Met. Powder Industries Fed., Priceton, New
Jersey, (1980)102-105.
[12] S.lhang, L. Lu and M.O. Lai; Mater. Sci. and Eng., AI71
(1993) 257-262.
[13] L. Lu. M.O. Lai and S. Zhang; Mater. Sci Techno!.,
10(1994) 319-322.
[14] lS. Benjamin and I.E. Volin; Metall. Trans., 5(1974)
1929·1934.
[15] W.G. Liu and CY. Chung; submitted to Powder
Metallurgy.