Materials Transactions, Vol. 45, No. 7 (2004) pp.

2443 to 2448
#2004 The Japan Institute of Metals

EXPRESS REGULAR ARTICLE

Mechanical Properties and Shape Memory Behavior of Ti-Nb Alloys

Hee Young Kim1 , Hashimoto Satoru1 , Jae Il Kim1 , Hideki Hosoda2 and Shuichi Miyazaki1 *
1
2

Institute of Materials Science, University of Tsukuba, Tsukuba 305-8573, Japan

Precision and Intelligent Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan

Mechanical properties and shape memory behavior of Ti-(2029)at%Nb alloys were investigated in order to develop Ni-free biomedical
shape memory alloys. The Ti-Nb alloys were fabricated by arc melting method. The ingots were cold-rolled with a reduction up to 95% in
thickness and then solution treated at 1173 K for 1.8 ks. The martensitic transformation temperature decreased by 43 K per 1 at% increase of Nb
content. The shape memory eect and superelastic behavior were observed at room temperature in the Ti-(2225)at%Nb alloys and Ti-(25.5
27)at%Nb alloys, respectively. A small enthalpy of the martensitic transformation and a large dierence between Ms and Mf were observed in
the Ti-Nb alloys compared to Ti-Ni shape memory alloys. The maximum recovered strain of 3% was obtained at room temperature in solution
treated Ti-(2527)at%Nb alloys. The heat treatment at 573 K for 3.6 ks stabilized superelastic behavior of Ti-Nb alloys by increasing the critical
stress for slip.
(Received March 17, 2004; Accepted May 17, 2004)
Keywords: shape memory alloy, superelasticity, biomaterial, smart material, titanium based alloy

1.

Introduction

Shape memory alloys having good biocompatibility have

been required for biomedical applications. Ti-Ni shape
memory alloys have been successfully applied as biomedical
materials owing to their superior shape memory property,
superelasticity and corrosion resistance.1,2) However, the Nihypersensitivity and toxicity of Ni have been pointed out in
Ti-Ni alloys.3) In order to pursue absolute safety, the
development of Ni-free Ti-based shape memory alloys is
strongly required.
It has been well known that the
-type Ti alloys exhibit a
martensitic transformation from
(disordered BCC) to two
metastable martensite structures, either hexagonal martensite
(0 ) or orthorhombic martensite (00 ), by quenching. The
martensite structure changes from 0 to 00 above a critical
alloying content.46) The transformation strain from the
to
00 is accommodated primarily by internal twinning. The
shape memory eect is associated with the reversion of 00 to

in
-type Ti alloys. The martensitic transformation start
(Ms) temperature can be controlled by addition of alloying
elements. But, for the biomedical applications, alloy designs
including non-toxic elements are required. The shape
memory eect has been reported in Ti-Mo alloys710) and
Ti-V alloys.11) However, the Ti-Mo based alloys are
susceptible to ! phase embrittlement. The Ti-V alloys are
not suitable for biomaterial because of the cytotoxity of V.12)
Ti-Nb alloys exhibit shape memory eect. Baker reported the
shape memory eect in Ti-35 wt%Nb(Ti-21.7 at%Nb) alloy.13) Recently, the shape memory and superelastic behavior
in Ti-Nb-Sn alloys14,15) and Ti-Nb-Al alloys16) have been
reported. However, no systematic research on mechanical
property, shape memory eect and superelastic behavior was
reported in Ti-Nb binary alloys.
In this study, mechanical properties and shape memory
behavior of Ti-Nb alloys were investigated in order to
develop Ni-free biomedical shape memory alloys. The
eects of Nb content on mechanical properties and shape
*Corresponding

author, E-mail: miyazaki@ims.tsukuba.ac.jp

memory behavior were investigated by tensile tests at various

temperatures and thermal cycling tests under various constant
stresses. The eects of aging at low temperature on shape
memory eect and superelasticity were also investigated in
Ti-Nb alloys.
2.

Experimental Procedures

The Ti-(2029)at%Nb alloys were prepared by the Ar arc

melting method. The ingots were cold-rolled with the
reduction of 95% in thickness. The cold-rolled sheets were
cleaned with ethanol, wrapped in Ti foils and encapsulated in
quartz tubes under a 25 torr partial pressure of high-purity Ar,
and then heat treated at temperatures between 573 K and
1273 K for 60 s3.6 ks, respectively. The sheets were
quenched into water by breaking the quartz tubes. Specimens
for the mechanical tests were cut by an electro-discharge
machine. The damaged surface was removed by mechanical
polishing followed by eletro-polishing. Tensile tests were
carried out at a strain rate of 1:67
104 s1 at various
temperatures. The gage length of specimens was 20 mm.
Thermal cycling tests were carried out under various constant
stresses. XRD (X-ray diraction) measurements were conducted at room temperature with CuK to determine the
constituent phases. Si powders were used as a reference.
3.

Results and Discussion

Phase constitutions for Ti-(20-29)at%Nb alloys were

investigated by XRD after solution treatment at 1173 K for
1.8 ks. Typical examples of XRD proles obtained at room
temperature are shown in Fig. 1 for Ti-20 at%Nb, Ti24 at%Nb and Ti-28 at%Nb alloys subjected to the solution
treatment. All the peaks were identied as the 00 martensite
phase in the Ti-20 at%Nb alloy except peaks corresponding
to Cu and Si of specimen holder and standard sample
powders, respectively. The peaks from both 00 and
were
observed in the Ti-24 at%Nb alloy. The XRD prole from the
Ti-28 at%Nb alloy shows a single phase of
at room
temperature. These results indicate that the Ms temperature

H. Y. Kim, H. Satoru, J. I. Kim, H. Hosoda and S. Miyazaki

(211)

600

(200)

Stress, / MPa

Cu
Si
(131) "
(113) "

30

40

50

(130) "
60

600

Ti-25Nb

Ti-25.5Nb

Ti-26Nb

Ti-27Nb

Ti-28Nb

Ti-29Nb

400
200

600
400

Cu
Si

(022) "
Si

Cu

Si

(110) "
(020) "
(111) "
(021) "
Cu

Si
20

Ti-24Nb

Ti-24Nb

Ti-20Nb

Ti-23Nb

200

Cu

Ti-28Nb

Ti-22Nb

400

Si

(110)
Cu

Intensity (a.u.)

Si

Si

2444

70

80

200

2
0

Fig. 1 X-ray diraction patterns of Ti-20 at%Nb, Ti-24 at%Nb and Ti28 at%Nb obtained at room temperature in the solution treated condition of
1173 K for 1.8 ks.

Stress, / MPa

600

Strain, (%)
Fig. 3 Stress-strain curves obtained under loading and unloading for Ti(2229)at%Nb alloys subjected to the solution treatment at 1173 K for
1.8 ks.

Ti-28Nb
Ti-22Nb Ti-20Nb

400
Ti-26Nb Ti-24Nb

500
450

200

10

20

30

40

Strain, (%)
Fig. 2 Stress-strain curves of Ti-(2028)at%Nb alloys obtained at room
temperature after the solution treatment at 1173 K for 1.8 ks.

is lower than room temperature for the Ti-28 at%Nb alloy and
the Mf temperature is higher than room temperature for the
Ti-20 at%Nb alloy.
Figure 2 shows stress-strain curves of Ti-(2028)at%Nb
alloys obtained by tensile tests at room temperature after the
solution treatment at 1173 K for 1.8 ks. A large elongation of
40% was obtained in the Ti-20 at%Nb alloy. The elongation
decreased with increasing Nb content. The yield stress
decreased with increasing Nb content from 20 at% to 26 at%.
The Ti-26 at%Nb alloy exhibits double yielding. Figure 3
shows the series of stress-strain curves for Ti-(2229)at%Nb
alloys subjected to the solution treatment. Tensile stress was
applied until strain reached about 2.5%, and then the stress
was removed. After unloading, the specimens were heated at
about 500 K: broken lines with arrows indicate the shape
recovery by heating. The Ti-(2225)at%Nb alloys show the
shape memory eect. The superelastic behavior was observed in the Ti-(25.527)at%Nb alloys. The largest strain
recovered superelastically was obtained in the Ti-26 at%Nb
alloy. Neither shape memory eect nor superelastic behavior
was observed in the Ti-(2829)at%Nb alloys. Yield stresses
were evaluated using the stress-strain curves of the Ti-(20
29)at%Nb and they are plotted as a function of Nb content in
Fig. 4. The yield stress decreased with increasing Nb content

Critical Stress, /MPa

400

350
300
250
200
150
100
20

22

24

26

28

30

Nb content (at%)
Fig. 4 Nb content dependence of yield stress for Ti-(2029)at%Nb alloys
solution treated at 1173 K for 1.8 ks.

reaching a minimum yield stress around 26 at%Nb, and then

the yield stress increased rapidly from 27 to 28 at%Nb. It is
considered that the increase in yield stress with decreasing
Nb content for the Ti-(2025)at%Nb alloys is due to the
increase of stress for the reorientation of martensite variants.
The stress-strain curve of Ti-28 at%Nb exhibits a single
yielding as shown in Fig. 2, and no superelastic behavior was
observed during unloading. The Ms temperatures of Ti-(28
29)at%Nb alloys are lower than room temperature since the
XRD shows a single phase of
at room temperature. This
indicates that the stress for inducing martensite is higher than
that of the slip deformation due to dislocations in the Ti-(28
29)at%Nb alloys.
Figure 5 shows strain-temperature curves measured during
thermal cycling between 173 K and 423 K under constant
stresses for the Ti-26 at%Nb alloy subjected to the solution

Mechanical Properties and Shape Memory Behavior of Ti-Nb Alloys

600

1%

77K

193K

233K

253K

273K

293K

313K

333K

353K

Stress

400

Strain, (%)

400MPa

200
350MPa

Stress, / MPa

300MPa
250MPa
As

200MPa
150MPa
100MPa
50MPa

Af

Mf

Ms

Fig. 5 Stress-strain curves obtained at various temperatures for the Ti26 at%Nb alloy solution treated at 1173 K for 1.8 ks.

treatment at 1173 K for 1.8 ks. The test was performed in

such a way that the magnitude of the applied stress was
increased stepwise for each thermal cycle, using a same
specimen throughout the test. The solid and dashed lines
indicate heating and cooling processes, respectively. In this
gure, Ms, Mf , As and Af denote the start and nish
temperatures for martensitic transformation and its reverse
transformation, respectively. The temperature hysteresis (Af Ms) was measured as about 50 K at 200 MPa. The transformation temperature increased with increasing applied
stress. The Ms temperature is plotted as a function of applied
stress in Fig. 6. There is a linear dependence between the
critical stress for inducing martensitic transformation and test
temperature. This dependence is known as the ClasiusClapeyron relationship. The relationship is written as
follows,
d

H

S


dT
T "
"

where  is a uniaxial stress, " is a transformation strain,
H

is the enthalpy of the transformation per unit volume and
S

400
350
300
250
200
150
100
50
250

300

350

400
200

400

Temperature, T / K

0
200

600

600

400

300

200

Stress, / MPa

2445

400

Temperature, T / K
Fig. 6 Temperature dependence of yield stress for the Ti-26 at%Nb alloy
solution treated at 1173 K for 1.8 ks.

200
0

Strain, (%)
Fig. 7 Strain-temperature curves at constant stress for the Ti-26 at%Nb
alloy solution treated at 1173 K for 1.8 ks.

is the entropy of the transformation per unit volume. From

Fig. 6, the slop of the relationship, d=dT is determined to be
4.4 MPa/K. The Ms temperature under zero stress was
evaluated to be 260 K by extrapolating the relationship.
Taking " 0:03 and T 260 K, the enthalpy and entropy
are estimated to be 340 J/mol and 1:30 J/molK, respectively. These values are much smaller than those of Ti-Ni
based alloys. For instance, Takei et al.17) evaluated the
enthalpy and entropy to be 1;819 J/mol and 7:69 J/
molK, respectively, for a Ti-50.3 at%Ni single crystal. No
distinct transformation peak was obtained by a dierential
scanning calorimeter in the solution treated Ti-Nb alloys. The
reason is that the enthalpy of the martensitic transformation is
small and the dierence between Ms and Mf is large in the
Ti-Nb alloys.
Figure 7 shows a series of stress-strain curves obtained at
various temperatures for the Ti-26 at%Nb alloy after the
solution treatment at 1173 K for 1.8 ks. The specimens were
immersed and kept in liquid nitrogen or methanol whose
temperature was controlled by liquid nitrogen when the test
temperature was between 77 K and 273 K. When the test
temperature was above room temperature, the specimens
were kept in methanol heated using a pipe heater. The shape
memory eect was observed for the specimens deformed at
77-273 K. The residual strain after unloading was completely
recovered by heating to about 500 K. The superelastic
behavior was observed at both 293 K and 313 K. The largest
superelatic strain was observed at 293 K, although the
superelasticity is incomplete. The critical stresses for
apparent yielding were evaluated, and they are plotted as a
function of temperature in Fig. 8. The critical stress decreases
with increasing temperature in the temperature range
between 77 K and 193 K. This is because the stress for the
rearrangement of martensite variants increases with decreasing temperature. The minimum of the critical stress is
observed at 273 K. This value is similar to the Ms temper-

H. Y. Kim, H. Satoru, J. I. Kim, H. Hosoda and S. Miyazaki

600

400

500

350

Ms Temperature, T/K

Critical Stress, /MPa

2446

400

300

200

100

300

250

200

150

0
50

100

150

200

250

300

350

100

400

24

25

Temperature, T/K

ature of 260 K obtained from Fig. 6. On the other hand, the

critical stress increased with increasing temperature between
273 K and 353 K since the stress for inducing martensites
increases with increasing temperature. The superlastic strain
decreased with increasing temperature in the temperature
range between 293 K and 353 K as shown in Fig. 7. The
critical stress to induce the martensite increases with increasing temperature, while the critical stress for slip decreases with increasing temperature. Slip occurs if the stress
level for slip becomes lower than the stress to induce the
martensite. Thus, the strain by slip deformation increases
with increasing temperature, causing the recoverable strain to
decrease.
It is also important to note that the critical stress for
apparent yielding is almost constant at temperatures between
193 K and 273 K. This is probably due to the large temperature dierence between Ms and Mf in the Ti-26 at% alloy
subjected to the solution treatment. The Mf , As and Af under
zero stress were estimated to be 180 K, 210 K and 315 K,
respectively, from Fig. 5. This means that both martensite
and
phase coexist in the temperature range between 180 K
and 260 K. The shape memory eect was due to the stress
induced martensitic transformation or the rearrangement of
martensite variants during loading and the reverse transformation upon heating after unloading. It is considered that
the critical stress for apparent yielding at temperature
between 193 K and 273 K for the Ti-26 at%Nb alloy is
associated with the stress for inducing martensite phase from
the
phase rather than the stress for the rearrangement of
martensite variants, since the stress for the rearrangement of
martensite variants increases with decreasing temperature. In
the region T > Ms, with decreasing temperature to Ms, the
stress for inducing martensite phase decreases to a threshold
stress below which an applied stress does not induce the
martensitic transformation eectively. When the test temperature is below Ms, the
phase is unstable so that the
phase
easily transforms to the martensite phase under the threshold
stress. It is suggested that the constant critical stress at
temperatures between 193 K and 273 K is the threshold stress
for inducing martensite phase from the
phase below Ms.
Figure 9 shows the Nb content dependence of the Ms

27

28

29

30

Nb Content (at%)
Fig. 9 Eect of Nb content on Ms temperature for Ti-(2528)at%Nb
alloys.

600

Ti-25Nb

400
200
0

Stress, / MPa

Fig. 8 Critical stress for apparent yielding determined from stress-strain

curves in Fig. 7.

26

600

Ti-26Nb

400
200
0
600

Ti-27Nb

400
200
0

Strain, (%)

2%

Fig. 10 Stress-strain curves obtained by cyclic loading-unloading tensile

tests for Ti-(2527)at%Nb alloys solution treated at 1173 K for 1.8 ks.

temperature in Ti-Nb alloys subjected to the solution treatment at 1173 K for 3.6 ks. The temperature exhibiting the
minimum critical stress was taken as Ms temperature. The Ms
temperature linearly decreases with increasing Nb content.
The Ms temperature decreased by 43 K with 1 at% increase of
Nb content.
Figure 10 shows stress-strain curves of Ti-(2527)Nb alloys subjected to the solution treatment at 1173 K for
1.8 ks. Each stress-strain curve and strain recovery were obtained at room temperature by a loading and unloading cycle
followed by heating. The similar measurement was repeated
by increasing the maximum strain upon loading in a same
sample for each alloy. The starting points of the stress-strain

Mechanical Properties and Shape Memory Behavior of Ti-Nb Alloys

curves are shifted in order that they are separated each other
to be distinguishable. The Ti-25 at%Nb alloy exhibited the
shape memory eect. On the other hand, the superelastic behavior was observed in the Ti-26 at%Nb and Ti-27 at%Nb alloys at the rst cycle. The magnitude of recovered strain, i.e.
the summation of superelstically recovered strain and recovered strain by heating up to the Af temperature, was plotted as
a function of tensile strain in Fig. 11. The Ti-(2527)at%Nb
alloys reveals almost same dependence of recovered strain on
tensile strain. The perfect recovery was exhibited up to about
2% strain. The permanent strain increased with increasing
tensile strain. The maximum recovered strain of 3% was obtained at about 5% tensile strain.

5
Ti-25Nb
Ti-26Nb
Ti-27Nb

Recovery Strain, (%)

2447

The Ti-(2527)at%Nb alloys were heat treated at 573 K for

3.6 ks after the solution treatment in order to precipitate ne 
phase. Figure 12 shows the stress-strain curves obtained by
cyclic tensile tests of the Ti-(2527)at%Nb alloys subjected
to heat treatment at 573 K. It is obvious that the critical stress
for the rst yielding increases when compared with the
solution treated specimens. This means that the critical stress
for inducing martensites increased by the heat treatment at
573 K. Figure 12 shows that almost perfect superelastic
behavior was obtained within a tensile strain of about 2.5%
for the Ti-26 at%Nb and Ti-27 at%Nb alloys. Figure 13
shows the magnitude of recovered strain for the Ti-(25
27)at%Nb alloys. When the specimen was heated above Af
temperature after deforming up to 3% strain followed by
unloading, only 0.2% strain remained for the Ti-26 at%Nb
and Ti-27 at%Nb alloys. The maximum recovered strain of
3.4% was obtained although the recovery rate decreased with
increasing tensile strain. The recovered strain and remained
plastic strain for the Ti-26 at%Nb alloy are plotted as a
function of applied stress in Fig. 14. The critical stress for slip
was dened as a stress inducing 0.5% plastic strain. The

Ti-25Nb
Ti-26Nb
Ti-27Nb

0
0

Tensile Strain, (%)

Fig. 11 Recovered strain as a function of tensile strain obtained by cyclic
loading-unloading tensile tests for Ti-(2527)at%Nb alloys solution
treated at 1173 K for 1.8 ks.

Recovery Strain, (%)

0
1

600

Tensile Strain, (%)

Ti-25Nb

400

Fig. 13 Recovered strain as a function of tensile strain obtained by cyclic

loading-unloading tensile tests for Ti-(2527)at%Nb alloys which were
aged at 573 K for 3.6 ks.

200

600

Ti-26Nb

Remained plastic strain : ST

Remained plastic strain : ST+Aging
Recovered strain : ST
Recovered strain : ST+Aging

400
3

200

Strain, (%)

Stress, / MPa

0
600

Ti-27Nb

400

200
0

0
0

Strain, (%)

2%

Fig. 12 Stress-strain curves obtained by cyclic loading-unloading tensile

tests for Ti-(2527)at%Nb alloys which were aged at 573 K for 3.6 ks.

100

200

300

400

500

600

700

800

Stress, /MPa
Fig. 14 Eect of aging at 573 K for 3.6 ks on the recovered strain and
remained plastic strain for Ti-26 at%Nb alloy.

2448

H. Y. Kim, H. Satoru, J. I. Kim, H. Hosoda and S. Miyazaki

critical stress for slip was obtained as 390 MPa and 520 MPa
for the solution treated specimen and the aged specimen,
respectively. As a result, the higher critical stress for slip
resulted in the stable superelastic behavior in the aged
specimens. It is suggested that the increase of critical stress
for slip is due to the precipitation of  phase during aging. It
is also important to note that the shape memory eect and
superelastic behavior of Ti-Nb alloys can be improved by
heat treatment. But, the systematic research including microstrucutral observation is required to clarify the eect of aging
treatment on transformation and mechanical properties of TiNb alloys. Based on the above results, it can be concluded
that Ti-Nb alloys are promising for the biomedical shape
memory and superelastic alloys. Further research on the
eect of alloying element and thermo-mechanical treatment
on the mechanical properties is needed to improve the shape
memory and superelastic properties of Ti-Nb alloy systems.
4.

Conclusions

(1) The martensitic transformation start temperature (Ms)

decreased by 43 K with 1 at% increase of Nb content. The
shape memory eect and superelastic behavior were observed in Ti-(2225)at%Nb alloys and Ti-(25.527)at%Nb
alloys, respectively, subjected to solution treatment at 1173 K
for 3.6 ks, respectively. Neither shape memory eect nor
superelastic behavior was observed in Ti-(2829)at%Nb
alloys.
(2) The critical stress for inducing martensitic transformation
increased with increasing test temperature. The enthalpy and
entropy for the martensitic transformation were estimated to
be 340 J/mol and 1:30 J/molK, respectively.
(3) The maximum recovered strain of 3% was obtained at
room temperature in the solution treated Ti-(2527)at%Nb
alloys. The low critical stress for slip deformation caused the
superelasticity not to reveal a large strain. The aging
treatment at 573 K for 3.6 ks increased the critical stress for
slip and stabilized the superelastic behavior of Ti-Nb alloys.

Acknowledgments
This work was partially supported by the 21 Century
Center of Excellence Program and the Grants-in-Aid for
Fundamental Scientic Research (Kiban A (19992001),
Kiban A (20022004)) from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
REFERENCES
1) Y. Oshida and S. Miyazaki: Corrosion Engineering 40 (1991) 1009
1025.
2) M. Semlitsch, F. Staub and H. Webber: Biomed. Tech. 30 (1985) 334
339.
3) S. Shabalovskaya, J. Cunnick, J. Anderegg, B. Harmon and R.
Sachdeva: Proc. First Inter. Conf. Shape Memory and Superelastic
Technologies, (SMST, 1994) pp. 209215.
4) R. Davis, H. M. Flower and D. R. F. West: Acta Metall. 27 (1979)
10411052.
5) T. Ahmed and H. J. Rack: J. Mater. Sci. 31 (1996) 42674276.
6) R. Davis, H. M. Flower and D. R. F. West: J. Mater. Sci. 31 (1979) 712
722.
7) W. F. Ho, C. P. Ju and J. H. Chern Lin: Biomaterials 20 (1999) 2115
2122.
8) T. Grosdidier and M. J. Philippe: Mater. Sci. Eng. A291 (2000) 218
223.
9) H. Hosoda, N. Hosoda and S. Miyazaki: Trans. MRS-J 26 (2001) 243
246.
10) H. Y. Kim, Y. Ohmatsu, J. I. Kim, H. Hosoda and S. Miyazaki: Mater.
Trans. 45 (2004) 10901095.
11) T. W. Duerig, J. Albrecht, D. Richter and P. Fischer: Acta Metall. 30
(1982) 21612172.
12) S. G. Steinemann: Evaluation of Biomaterials, Ed. by G. D. Winter,
J. L. Leray and K. de Goot, (Jhon Wiley & Sons, Ltd., 1980) 134.
13) C. Baker: Metal Sci. J. 5 (1971) 92100.
14) K. Nitta, S. Watanabe, N. Masahashi, H. Hosoda and S. Hanada:
Structural Biomaterials for the 21st Century, TMS, 2001, pp. 2534.
15) E. Takahashi, T. Sakurai, S. Watanabe, N. Masahashi and S. Hanada:
Mater. Trans. 43 (2002) 29782983.
16) H. Hosoda, Y. Fukui, T. Inamura, K. Wakashima and S. Miyazaki and
K. Inoue: Mater. Sci. Forum 426432 (2003) 3121.
17) F. Takei, T. Miura, S. Miyazaki, S. Kimura, K. Otsuka and Y. Suzuki:
Scr. Metall. 17 (1983) 987992.