Materials Transactions, Vol. 47, No. 3 (2006) pp.

716 to 719
Special Issue on Shape Memory Alloys and Their Applications
#2006 The Japan Institute of Metals

Effects of Cerium Addition on Martensitic Transformation

and Microstructure of Ti49:3 Ni50:7 Alloy
Wei Cai* , Ailian Liu, Jiehe Sui and Liancheng Zhao
School of Materials Science and Engineering, P. O. Box 405, Harbin Institute of Technology, Harbin, 150001, P. R. China

In order to study the effect of Cerium on martensitic transformation and microstructure of Ti49:3 Ni50:7 alloy, a group of TiNiCe alloys with
different content of Ce addition were prepared. The microstructure and the martensitic transformation behavior of TiNiCe ternary alloys were
investigated by optical microscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC).
The results show that the microstructure of Ti49:3 Ni50:7 alloy is changed obviously by Ce addition, and there are many Ce-rich phases dispersing
in the TiNi matrix. One step martensitic transformation due to B2 $ B190 transformation occurs during the cooling and heating processes of the
TiNiCe ternary alloys. The phase transformation temperatures increase remarkably when the content of Ce is less than 2 at%. However, when the
content of Ce is further increasing, the phase transformation temperatures increase slowly and tend to stable.

(Received September 20, 2005; Accepted January 6, 2006; Published March 15, 2006)
Keywords: TiNiCe shape memory alloy, microstructure, martensitic transformation

1. Introduction quench with breaking the capsules. Following the above

TiNi alloys are the most important shape memory alloys
(SMAs) because of their shape memory effect (SME) and
pseudoelasticity (PE). It has been confirmed that the proper-
ties of TiNi SMAs can be affected by various thermal
mechanical treatments such as aging in Ni-rich TiNi
alloys,1–3) cold rolling4) and thermal cycling,5) moreover,
the addition of a third element to replace Ni and/or Ti has a
substantial effect on phase transformation behavior of TiNi
binary alloys. It is well known that the Ms temperature
decreases with the addition of V, Fe, Co, but increases
remarkably with element such as Au, Pd, Pt, and Hf.6–8)
Rare earth elements are widely used as alloying element to
ferrous, non-ferrous alloys to refine the grain, purify the grain
boundaries and improve the mechanical properties. It has
been found that the martensitic transformation temperatures
can be increased rapidly with rare earth Ce and Dy,9,10) but
the effect of Ce on martensitic transformation of Ni-rich TiNi
alloys isn’t clear up to now. The purpose of the present work
is to investigate the effect of Ce addition on the micro-
structure and martensitic transformation of Ti49:3 Ni50:7
alloys.
2. Experimental
A group of TiNiCe alloys were prepared by a non-
consumable arc-melting furnace using a water-cooled copper
crucible, and the symbols Ce0, Ce05, Ce1, Ce2 andCe5 are
hereinafter used to denote specimens of Ti49:3 Ni50:7 ,
Ti49:05 Ni50:45 Ce0:5 , Ti48:8 Ni50:2 Ce1 , Ti48:3 Ni49:7 Ce2 , Ti46:8 -
Ni48:2 Ce5 , respectively. Sponge Ti (99.97 mass%), electro-
lytic Ni (99.97%) and Ce (99.95 mass%), totaling about
100 g, were melted and re-melted for six times in an argon
atmosphere. A pure titanium button was also melted and used
as an oxygen getter during the arc melting. The specimens
were spark-cut from the ingots and solution-treated at 900
C
for an hour in evacuated quartz capsules followed by a water
*Corresponding author, E-mail: weicai@hit.edu.cn, liuailian@hit.edu.cn
procedure, they are mechanically polished, then etched in a
solution consisting of 10 pct HF, 20 pct HNO3 and 100 pct
H2 O (by volume).
The phase transformation temperatures of TiNiCe alloys
were determined by differential scanning calorimetry (DSC)
using Perkin-Elmer Diamond DSC. The temperature range of
heating/cooling process investigated is from 150 to 180
C
with a heating/cooling rate of 20
C/min. Tangent lines in the
DSC curve were made to determine the phase transformation
temperatures. Microstructure observations were made using
an Olympus metallographic microscope and CamScan
MX2600FE Scanning electron microscopy (SEM) equipped
with energy dispersive X-ray (EDX) analysis systems made
by Oxford. The phase analyses were carried out using Rigaku
D/max-rb rotating anode X-ray diffractometer with a graph-
ite monochromator and Cu K
radiation,  ¼ 0:15405 nm.
3. Results and Discussion
3.1 Optical microstructure
Figure 1 shows the optical microstructure of Ce2 and Ce5
alloys. It is well known that the microstructure of TiNi alloy
is single phase. It can be seen that the microstructure of
TiNiCe ternary alloy is obviously different from that of TiNi
binary alloy. There are many black particles formed with
Cerium addition. In Ce5 alloy the size of black particles
grows apparently, and the black particles have a tendency to
interconnect.
3.2 SEM microstructure
In order to further clarify the composition of the black
phase observed in Fig. 1, the back scattering image are taken
by SEM as shown in Fig. 2. It is clear that there are two
different contrast areas observed, including the white phases
and the black matrix. According to its distribution and
morphology, the white phase dispersing in the black matrix is
the black particle observed in Fig. 1. It can be seen that when
the concentration of Ce is increasing from 0.5 to 5 at%, the
amount and the size of white phases are both increase. The
 Effects of Cerium Addition on Martensitic Transformation and Microstructure of Ti49:3 Ni50:7 Alloy 717

a b

50µm 50 µm

Fig. 1 Optical microstructure of Ce2 and Ce5 alloys a) Ce2 b) Ce5.

a b

c d

Fig. 2 The back scattering image of TiNiCe alloys a) Ce05 b) Ce1 c) Ce2 d) Ce5.

average size of the white phase is about 0.5–25 mm depending

on Ce concentration. Table 1 The composition analysis of white phase and the matrix of TiNiCe
Because the scattering amplitude of the back scattering alloys.
electron is proportional to the atomic number of the
Ti Ni Ce
individual element, the white phase in Fig. 2 indicates the Alloy Phase
(at%) (at%) (at%)
region of the higher concentration of Ce. Table 1 is the EDS
Ce0 the matrix 50.46 49.54 —
analysis of the white phase and the matrix of TiNiCe alloys.
the matrix 50.67 49.33 0
With Ce addition increasing, the concentration of Ti Ce05
white phase 10.745 45.355 43.85
increases whereas that of Ni decreases in the matrix, which
the matrix 50.71 49.29 0
means that Ce addition alternates the composition of the Ce1
white phase 10.87 45.31 43.82
matrix and makes Ti richer in the matrix than that in the
the matrix 50.81 49.19 0
matrix of Ti49:3 Ni50:7 alloy. In the white phase, the ratio of Ce2
white phase 14.38 44.14 41.48
Ce/Ni in the white phase is approximate 1. According to the
the matrix 51.125 48.875 0
Ce–Ni binary phase diagram the Ce-rich phase may be CeNi Ce5
white phase 2.91 47.14 49.95
intermetallics.
718 W. Cai, A. Liu, J. Sui and L. Zhao

(012)M
(111)M

(020)M
3000 (002)M
Intensity, drb

(110)M

2000
(110)B2

(112)M

(003)M
Ce5

1000
Ce2

Ce05
0 Temperature, °C

40° 50° 60° 70° 80°

Fig. 4 DSC curve of Ti49:3x=2 Ni50:7x=2 Cex alloys.
2θ

Fig. 3 X-ray diffraction curves of TiNiCe alloys. Table 2 Phase transformation temperatures of TiNiCe alloys.

Alloy Ms/
C Mf/
C As/
C Af/
C

Ce0 46:5 66 38 24
3.3 X-ray diffraction results
Ce0.5 25.5 18 48 71
Figure 3 shows the X-ray diffraction curves of Ce05, Ce2
Ce1 48 28 66 91.5
and Ce5 alloys. Several martensite diffraction peaks appear,
Ce2 65 58 91 100
i.e., (020)M , ð11
1ÞM , (002)M , and (111)M peaks, which
Ce5 77 68 101 114
indicate Ce2 and Ce5 alloy are in martensite state at room
temperature and the lattice type of martensite is B190 , the
same as that of binary Ti–Ni alloy. With the content of Ce
addition increasing, the intensity of the characteristic peaks 80
1.05
of martensite becomes higher, and the width of the peaks
60
increases. This means the martensitic lattice is distorted by

The ratio of Ti/Ni in the matrix

Ce addition, and the more amount of Ce addition, the more 40 1.04
Temperature,°C

distortion. When the content of Cerium is from 0.5 to 2 at%,

20
the diffraction angle 2 corresponding to a certain peak also
1.03
becomes smaller, which indicates the corresponding inter- 0

planar space of martensite increases. When Ce content is Ms temperature

-20
The ratio of Ti/Ni
from 2 to 5 at%, the diffraction angle 2 becomes bigger, 1.02

which indicates the interplanar space of martensite decreases. -40

Because the radius of Ce is much larger than that of Ti and

-60 1.01
Ni, when Ce atom is solubilized in the matrix, the martensitic 0 2 4 6

lattice is distorted certainly. Besides the peaks corresponding Ce concentration, at%

to martensite, there are many peaks, which must be related to

the Ce-rich phase. Though the ratio of Ce/Ni in Ce-rich
phase is approximate 1, the diffraction pattern does not agree
with the data in No. 19-0292 card of JCPDS (CeNi phase).
Ce-rich phase may be CeNi type ternary phase and its crystal
structure is needed for further research.
3.4 DSC result
Figure 4 shows the DSC curves of TiNiCe alloys and their
corresponding phase transformation temperatures are listed
in Table 2. There is only one peak due to B2 $ B190
transformation observed during the heating/cooling process
of the experimental alloys. This indicates one-step marten-
sitic transformation occurring in TiNiCe alloy, which is the
same with that of TiNi alloy, and Ce addition doesn’t change
the martensitic transformation type.
Figure 5 shows the effect of Ce content on Ms temperature
and the ratio of Ti/Ni in the matrix of the experimental
alloys. The phase transformation temperatures firstly increase
rapidly with Ce concentration increasing from 0.5 to 2 at%
and then increase slowly when Ce concentration is from 2 to
5 at%. It is seen that Ce addition changes the composition of
Fig. 5 Effect of Cerium concentration on Ms temperature and the ratio of
Ti/Ni in the matrix of TiNiCe alloys.
the matrix remarkable. The ratio of Ti/Ni in the matrix of
Ti49:3 Ni50:7 alloy and Ce05 alloy is 1.019 and 1.027,
respectively. It is well known that Ms temperature decreases
about 10
C when the content of Ni in matrix increases
0.1 at%. However, in fact the increase of Ms is about 70
C.
From above, it can be concluded that Ce addition not only
alternates the composition of the matrix of Ti49:3 Ni50:7 alloy
but also give an effect on the increase of martensitic
transformation temperatures.
4. Conclusion
Effects of different content of Ce addition on micro-
structure and transformation characteristics of Ti49:3 Ni50:7
alloys have been investigated. The results show that the
microstructure of Ti49:3 Ni50:7 alloy is changed obviously, and
many Ce-rich phases form and disperse in the matrix. The
martensitic lattice is distorted with Ce addition, and the
 Effects of Cerium Addition on Martensitic Transformation and Microstructure of Ti49:3 Ni50:7 Alloy
interplanar spaces of martensite firstly increase when Ce
content is less than 2 at% while decrease with more than
2 at% Ce addition. One step martensitic transformation due to
B2 $ B190 transformation occurs during the cooling/heat-
ing processes of the TiNiCe ternary alloys. When Ce content
is from 0.5 to 2 at%, the phase transformation temperatures
increase remarkably, and the more Ce added, the higher the
phase transformation temperatures. However, when the
content of Cerium is from 2 to 5 at%, the phase trans-
formation temperatures increase very slow and tend to stable.
Acknowledgement
This research is supported by the National Nature Science
Foundation of China, Grant No. 50471018. The authors are
also grateful to Mr. Jianfeng Sun, Heilongjiang Institute of
Science and Technology of China, for his help for the SEM
observation.
719
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