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Scripta Materialia 68 (2013) 10081011

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Thermal stability and high-temperature shape memory eect

of TiTaZr alloy
X.H. Zheng,a J.H. Sui,a, X. Zhang,a Z.Y. Yang,a H.B. Wang,b X.H. Tiana
and W. Caia,
a

National Key Laboratory Precision Hot Processing of Metals, School of Materials Science and Engineering,
Harbin Institute of Technology, Harbin 150001, Peoples Republic of China
b
Collage of Physics & Electronic Engineering, Taizhou University, Taizhou, 318000, Peoples Republic of China
Received 28 January 2013; revised 8 March 2013; accepted 8 March 2013
Available online 15 March 2013

The eect of Zr content on the thermal stability of martensite transformation and the shape memory eect of TiTa alloy was
investigated. Zr addition improved the thermal stability and shape memory eects of TiTa alloys. Ti20Ta10Zr alloy exhibited
good thermal stability with a peak martensite reverse transformation temperature of 763 K and a recovered strain of 4.6% with
8% pre-strain.
2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: TiTaZr alloys; High-temperature shape memory alloy; Martensitic transformation; Thermal stability

High-temperature shape memory alloys (HTSMAs) with a martensite transformation temperature

(Ms) of over 373 K are attractive materials for actuator
applications [1,2]. Therefore, much research has been focused on the development of HTSMAs, such as TiNi
X (X = Zr, Hf, Pd, Pt), NiAl, NiMn-based and Tibased alloys [1,36]. Among these alloys, the Ti-based
HTSMAs exhibit excellent cold workability, which
makes them easily formable into suitable sizes and
shapes. However, the x phase readily occurs in these alloys during thermal cycling, leading to brittleness, and
an unstable martensitic transformation temperature
and shape memory eect [7,8]. The thermal stability of
TiTa alloy is better than that of other b-type Ti-based
alloys with similar Ms temperatures, such as TiNb and
TiMo alloys [2]. Thus, much eort has been devoted to
suppressing the x phase precipitation and increasing the
stability of TiTa alloy by adding a ternary element into
TiTa alloys [9]. It has been reported that the Ti27Ta
5Al alloy exhibits a stable Ms of 443 K, but the Al
addition decreases the recovery strain to 1.5% [10]. Ti
20Ta3.5Sn also displays a stable Ms of 443 K with
a larger recovery strain of 3.2% compared with TiTa
binary alloy [11]. Therefore, higher shape memory eect

Corresponding

authors. Tel./fax: +86 451 86418649 (J.H. Sui);

e-mail addresses: suijiehe@hit.edu.cn; weicai@hit.edu.cn

and transformation temperature with excellent thermal

stability are expected to extend the application of Ti
Ta alloys in high-temperature environments.
Bo  Md diagrams have proved useful in the design
of Ti-based alloys in previous reports [12,13]. Bo is the
average bond order between atoms and Md is the
average d-orbital energy level of the elements in the
alloy. According to d-electron alloy theory, Zr has a
smaller Md value and a larger Bo value compared
with Ta [13,14]. It can be calculated that the value
of Bo decreases and Md increases with increasing Zr
content as a substitute of Ta in TiTa alloys; furthermore Zr addition leads to the b/a00 boundary in the
Bo  Md diagram moving to a higher temperature,
and far away from the x phase precipitation boundary. It has also been reported that the addition of
Zr into TiNb alloys can increase the critical stress
for slipping and shape memory eect [15]. Considering
the above factors, we added Zr into TiTa alloys and
investigated the eects of this addition on the thermal
stability and shape memory properties of TiTa alloys
in this study.
The TiTaZr alloys were prepared on a non-consumable arc-melting furnace under an Ar atmosphere
using a water-cooled copper crucible from elemental
constituents with a purity of 99.9%. The arc-melting
was repeated eight times to ensure uniformity of

1359-6462/$ - see front matter 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.scriptamat.2013.03.008

X. H. Zheng et al. / Scripta Materialia 68 (2013) 10081011

Figure 1. XRD patterns of TiTaZr alloys at room temperature.

composition. After melting, the ingots were homogenized at 1173 K for 6 h in vacuum-sealed quartz tubes,
and then quenched into ice water. Cold rolling was
performed up to 70% in thickness reduction. The
nal thickness of the specimen after cold rolling was
2 mm. The cold-rolled specimens were cut into the
desired shape for various characterizations by a sparkerosion machine. The specimens were sealed in a vacuum quartz tube. Solution treatment was carried out
at 1123 K for 1 h. The phase structure was identied
by X-ray diraction (XRD) on a Riguku-D/max-cB
X-ray diractometer with Cu Ka radiation at room temperature. The phase transformation temperature of the
specimens was determined by dierential thermal analysis (DTA) using a Mettler-Toledo TGA1600 with a heating/cooling rate of 20 K min1. The tensile stressstrain
tests were performed on an Instron 5569 machine with a

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strain rate of 102 min1. The dimension length and the

cross-section of the tensile samples were 40 mm and
3 mm  1 mm, respectively.
Figure 1 shows the XRD patterns of TiTaZr alloy
at room temperature. According to the XRD results,
the crystal structures can be indexed by the orthorhombic martensite without any other phases, which means
the Ms temperature is above room temperature and Zr
atoms are dissolved into the martensite lattice. The
unit-cell volume of TiTaZr alloys is increased with
increasing Zr content because of the larger atomic radius
of Zr (0.16 nm) compared with that of Ta (0.147 nm).
Figure 2ac shows the DTA curves of TiTaZr alloys
with dierent thermal cycles. Figure 2a only shows the
martensite reverse transformation of Ti30Ta alloy because the martensite transformation of Ti30Ta cannot
be detected by DTA. A similar phenomenon was also
noted in other reports [2,16]. It can be seen that the transformation temperature increases with increasing Zr content, which is due to decreasing b-stability element Ta
content. In order to investigate the thermal stability of
TiTaZr alloys, the peak temperature of the martensite
reverse transformation (Ap) was used to evaluate the
thermal stability. Figure 3d shows the dependence of
transformation temperatures on the thermal cycling
number. The Ap temperature of Ti30Ta alloy signicantly decreases from 483 to 461 K after ve thermal cycles. The decrease in Ap is due to the precipitation of x
phase, which has been reported in previous papers
[2,8,9]. With addition of 5 at.% Zr, the decrease in Ap
is about 13 K, which is smaller than that of Ti30Ta binary alloy. It should be noted that the Ti20Ta10Zr alloy

Figure 2. The DTA curves of TiTaZr alloys with dierent thermal cycles (ac) and the transformation temperatures as a function of thermal
cycling number for TiTaZr alloys (d).

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X. H. Zheng et al. / Scripta Materialia 68 (2013) 10081011

Figure 3. (a) Stressstrain curves of TiTaZr alloys. (b) Stressstrain curves obtained upon loading and unloading.

exhibits good thermal stability, and the Ap and Mp are

almost unchanged after ve thermal cycles. It can be concluded that the addition of Zr improves the transformation temperature and stability of the TiTa alloys.
It is generally accepted that the phase stability is related to the number of valence electrons per atom (e/
a), and more stable a00 phase can be obtained at room
temperature by appropriately decreasing the e/a of
b-Ti alloy [17,18]. It is well known that Zr is a neutral
element with a valence electron number of 4, and hence
the e/a value decreases when using Zr element as a
substitute for Ta (valence electron number 5) in TiTa
alloys, leading to an increase in the stability of a00 phase
and transformation temperature as well as avoiding the
precipitation of x phase.
Figure 3a shows the stressstrain curves of TiTaZr
alloys. It can be seen that the tensile stress increases and

the fracture strain decreases with increasing Zr content.

It also can be observed that the Ti25Ta5Zr and Ti
20Ta10Zr alloys exhibit two-stage yielding. The Ti
25Ta5Zr and Ti20Ta10Zr alloys are martensite
phase according to the room-temperature XRD and
DTA results, and therefore the two stages correspond
to the reorientation of the martensite variants and plastic deformation. However, the Ti30Ta alloy only displays one-stage yielding in the stressstrain curve. This
is probably due to the lower critical stress of plastic
deformation in the Ti30Ta alloy, which makes it easy
to induce plastic deformation during the reorientation
of the martensite variants. Thus martensite variant
reorientation and plastic deformation cannot be distinguished from the stressstrain curve of Ti30Ta alloy.
Figure 3b shows the loadingunloading curves of Ti
TaZr alloys with 6% pre-strain at room temperature.

Figure 4. (ac) Stressstrain curves obtained by cyclic loadingunloading tensile tests for TiTaZr alloys. (d) The stress dependence of the recovered
strain and remaining plastic strain for Ti20Ta10Zr.

X. H. Zheng et al. / Scripta Materialia 68 (2013) 10081011

The shape memory eect (SME) of TiTaZr alloys increases with increasing Zr content. The Ti20Ta10Zr
alloy displays the maximum SME of 2.8% with a recovery rate of 73%, which is higher than that of Ti30Ta alloy with a recovery rate of 51%.
Figure 4ac shows the stressstrain curves of TiTa
Zr alloys obtained from cyclic tensile testing. The stress
strain and strain recovery curves were obtained by loading and unloading at room temperature and heating
above Af. The measurements were repeated with
increasing pre-strain for the same sample. The residual
strain increases with increasing pre-strain, while the
SME rst increases and then decreases with increasing
pre-strain. The Ti20Ta10Zr alloy displays a perfect
recovery strain of 2% and a maximum recovery strain
of 4.6% with 8% pre-strain. The magnitude of SME,
recovery strain and plastic strain of Ti20Ta10Zr alloy
is plotted as a function of applied stress in Figure 4d. It
has been reported that the critical stress for slip (rs) is
dened as a stress inducing 0.5% plastic strain [8,19].
The rs for Ti20Ta10Zr and Ti30Ta alloy are 769
and 627 MPa, respectively. The rs increases with
increasing Zr content due to solution hardening. The
higher rs of Ti20Ta10Zr alloy makes it relatively
dicult to induce plastic deformation compared with
Ti30Ta alloy. This demonstrates that the Zr addition
can eectively increase recovery strain. The dashed lines
indexed in Figure 4ac show the tensile stress with 8%
pre-strain obtained from Figure 3a. It can be seen from
Figure 4a that the stress of Ti30Ta alloy is markedly
increased after tensile thermal cycles. Generally speaking, the x phase leads to higher Youngs modus and
hardness. Thus the increased stress of the Ti30Ta alloy
may be ascribed to precipitation of x phase [15]. The
amount of increase in the stress of Ti25Ta5Zr is
smaller than that of Ti30Ta alloy. In particular, there
is almost no change in stress after four tensile thermal
cycles of the Ti20Ta10Zr alloy. This indirectly indicates that the precipitation of x phase has been
suppressed.
In conclusion, the thermal stability and shape memory properties of TiTaZr HTSMAs were investigated.
The results demonstrate that the martensite transformation and shape memory eect increase with increasing Zr
content. The Ti20Ta10Zr alloy also shows good thermal stability and shape memory eect with the maximum recovery strain of 4.6% with 8% pre-strain.
Therefore, the Ti20Ta10Zr alloy is thought to be the
good candidate for a HTSMA.

1011

This work is supported by Natural Science

Foundation of China (Nos. 51071059, 51271065 and
51271069), the Major State Basic Research Development Program of China (973 Program) (No.
2012CB619400), Program for New Century Excellent
Talents in University of Ministry of Education of China
and Zhejiang Provincial Natural Science Foundation of
China (No. Y4100618).
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