DESIGN OF LOW ELASTIC MODULUS Ti-Nb-Zr ALLOYS FOR IMPLANT

MATERIALS
XIPING SONGa,*, LI YOUa, BEI ZHANGb, ANNA SONGc

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The State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing,
Beijing 100083, Peoples Republic of China
b
The School of Applied Science, University of Science and Technology Beijing
Beijing 100083, Peoples Republic of China
c
Department of Materials Science and Technology, Beijing University of Chemical Technology
Beijing 100029, Peoples Republic of China
*
xpsong@skl.ustb.edu.cn

Received 21 July 2010

Revised 20 December 2010
Titanium alloys are expected to be much more widely used for hard tissue implant materials due to
their superior biocompatibility and high corrosion. However, the larger Youngs modulus of present
titanium alloys always leads to stress shielding and harmful effects on human bones and results in
premature failure of the implant. Recently a d-electron alloy design method has been proposed to
design low elastic modulus titanium alloys and achieve some actual results. In this paper, a series of
the Ti-Nb-Zr alloys has been designed with the d-electron alloy design method, and the phase
structure, lattice parameter and elastic modulus have been investigated. The results show that with
the increase of
and , the lattice parameters of these alloys increase monotonously with the
single phase structure of bcc phase. The maximum increment reaches 4.5% compared with that of
matrix phase. As the
and
increase up further, the phase structure begins to change from bcc
phase to hcp phase. Correspondingly the elastic modulus decreases first and then increase, from
96.8 GPa to 67.4 GPa, and then to 83.2GPa with the increase of
and . The lattice parameter
and phase structure both exhibit significant influences on the elastic modulus of these alloys.
Keywords: Titanium alloys; elastic modulus; implant materials.

1. Introduction
Titanium alloys have been widely used for hard tissue implant materials due to their
excellent biocompatibility and high corrosion. However, the Youngs modulus of present
titanium alloys is much larger than that of a human bone, which will lead to stress
shielding and harmful effects in the vicinity of the implant area. Therefore, how to reduce
the elastic modulus of titanium alloys is of the great concern. Recently, Kuroda et al.1
have developed some new titanium quaternary alloys, Ti-Nb-Ta-Zr, Ti-Nb-Ta-Mo and
Ti-Nb-Ta-Sn, with low elastic modulus of about 50GPa based on the d-electron alloy
design method proposed by Morinaga et al.2 This result indicates a new research
direction in the development of titanium alloys with low elastic modulus. In this work,
a series of Ti-Nb-Zr alloys were designed based on the d-electron alloy design method
and their elastic modulus variation with the Nb and Zr additions were evaluated. The
334

Design of Low Elastic Modulus Ti-Nb-Zr Alloys for Implant Materials

335

lowest elastic modulus in Ti-Nb-Zr alloys and applicability of this design method will be
both discussed with the experimentally results.

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2. Experimental Method
A d-electron alloy design method is originally called the molecular orbital method (DV
X cluster method3). Based on this method, the electronic structures of bcc Ti alloyed
with a variety of elements can be calculated, and two alloying parameters of Bo and Md
can be deduced theoretically. The Bo is the bond order, which is the covalent bond
strength between Ti and an alloying element. The Md is the metal d-orbital energy level,
which correlates with the electro negativity and the metallic radius of elements. These
parameters are listed in Table 1 for various alloying elements in Ti.3 By taking the
compositional average of Bo and Md of the alloys (atom%), which are denoted as
and
respectively, the phase structure of the alloys can be predicted through the
and
diagram (see Figure1).
Table 1. List of Bo and Md values for bcc Ti.
3d Element

Bo

Md

Ti

2.790

2.447

4d Element
Zr

Bo

Md

5d Element

3.086

2.934

Hf

Bo

Md

3.110

2.975

2.805

1.872

Nb

3.099

2.424

Ta

3.144

2.531

Cr

2.779

1.478

Mo

3.063

1.961

3.125

2.072

Mn

2.723

1.194

Tc

3.025

1.294

Re

3.061

1.490

Fe

2.651

0.969

Ru

2.704

0.859

Os

2.980

1.018

Co

2.529

0.807

Rh

2.736

0.561

Ir

3.168

0.677

Ni

2.412

0.724

Pd

2.208

0.347

Pt

2.252

0.146

Cu

2.114

0.567

Ag

2.094

0.196

Au

1.953

0.258

It is reported that the least stable -phase alloys always exists in the phase boundary
of the /++(). And the stability of -phase has a general correlation with the elastic
property,4-5 i.e. the least stable phase the lowest Youngs modulus. Thus by design the
least stable phase alloy, the lowest Youngs modulus can be obtained.
In this paper, a series of titanium alloys, Ti62Nb38, Ti52Nb30Zr18, Ti46Nb24Zr30,
Ti35Nb15Zr50, Ti27Nb8Zr65 and Ti18Zr82 (mass%) alloys were prepared by argon arc
melting, and their
and
values were calculated and marked in
and
diagram,
see Fig.1 and Table 2. The position of these alloys appears along the phase boundary of
the /++() in the
and
diagram.
The elastic moduli of these alloys were determined by a Nano Intender (MTS). The
phase structure and lattice parameter of these alloys were also indentified by an X ray
diffraction method.

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X. P. Song et al.

Fig. 1. The phase stability index diagram based on

and parameters. Dash line is taken from M.
Morinaga,2 dash dot line is taken from M. Abdel-Hady.4 The dash line and dash dot line both are the boundary
of phase to phase. The designed alloys are shown by the solid circles.
Table 2. The nominal composition of experimental alloys (mass.%) and their
Alloys

and

values.

Ti62Nb38

Ti52Nb30Zr18

Ti46Nb24Zr30

Ti35Nb15Zr50

Ti27Nb8Zr65

Ti18Zr82

2.864

2.887

2.905

2.936

2.965

2.997

2.441

2.501

2.545

2.630

2.704

2.788

3. Results and Discussion

3.1. Phase structure and lattice parameter
Fig. 2 shows the XRD profiles of these alloys. It can be seen that the Ti62Nb38 alloy has
a single bcc phase structure, with the lattice parameter a=3.2911A. With the increase of
and
, the phase structure remains unchanged, but the lattice parameter increase,
from 0.7% increment to 4.5% increment compared with that of the basetitanium, see
Table 3. As the
and
increase up to that of Ti18Zr82 alloy, the single bcc phase
structure begins to change and form a single hcp phase.
Table 3. Lattice parameters variation of the designed phase titanium alloys.
Alloys

Ti62Nb38

Ti52Nb30Zr18

Ti46Nb24Zr30

Ti35Nb15Zr50

Ti27Nb8Zr65

titanium

a(A)

3.2911

3.3298

3.3538

3.4109

3.4533

3.3058

0.0240(0.7%)

0.0480(1.5%)

0.1051(3.2%)

0.1475(4.5%)

Deviation -0.0147

Design of Low Elastic Modulus Ti-Nb-Zr Alloys for Implant Materials

Ti62Nb38

Ti52Nb30Zr
18

34

337

Ti46Nb24Zr

30
5
4

Ti35Nb15Zr

1 2

20

30

40

50

2-Theta(

60

70

Fig. 2. XRD profiles of the designed alloys.

3.2. Nano elastic modulus

Fig. 3 shows the nano elastic modulus of these alloys in the 3D form. It can be seen that
with the increase of
and
, the nano elastic modulus decreases, from 96.8 GPa to
67.4 GPa, and as the
and
increase further, however, the nano elastic modulus
begins to increase in the opposite manner. The nano elastic modulus of Ti18Zr82 alloy
reaches 83.2GPa as the result.
100

1 1Ti62Nb38

2 Ti52Nb30Zr18

95

3 Ti46Nb24Zr30

90

5 Ti27Nb8Zr65

dulus
Nano elestic mo

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80

4 Ti35Nb15Zr50
6 Ti18Zr82

85
80

2
3

75

4
5

70
65
2.4

3.00
2.95

2.5

2.6
Md

2.90

2.7
2.8

2.85

Fig. 3. A 3D nano elastic moduli diagram with

Bo

and

parameters.

It has been reported that elastic modulus changes with the type of the phase existing
in the titanium alloys.6 The phase is considered to have the highest Youngs modulus,
the martensite and have lower modulus than that of phase, and the phase has the
lowest Youngs modulus among all these phases in titanium alloys. So select the phase
titanium alloys will be possible to reach the lower elastic modulus. In Ti-Nb-Zr ternary
alloys, Nb and Zr are stabilize elements, thus the alloys tend to be phase and exhibit
lower elastic modulus. As the Nb content decrease, the role of Zr in stabilizing phase
become weak. The alloys turn to be phase, resulting in an increase of elastic modulus.
As we know, elastic modulus of a material is regarded as a measure of the atomic
bond strength. The stronger the atomic bonds, the larger the elastic modulus of materials.
With the increase of lattice parameter, we had found that the nano elastic modulus

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338

X. P. Song et al.

decreased. So it can be concluded that with the increase of lattice parameter, the atomic
bond strength decrease, which cause the decrease of the elastic modulus. It has been
reported that the elastic modulus is not only related to the crystal structure, but also to the
interatomic distances in the crystal lattice.7 The variation of lattice parameter in titanium
alloys is always related with the variation of alloy element. So the elastic modulus can be
controlled by either alloying or phase transformation in the titanium alloys.
Thus, it is reasonable to accept the d-electron alloy design method in designing the
low elastic modulus titanium alloys. Although it contains the information of electronic
structure of atom, it indeed reflects the visible and detecting changes of alloys, such as
phase structure and lattice parameters. In this paper, it reveals a satisfied match in theory
design and experimental data, and provides one additional proof in its development.
4. Conclusion
The d-electron alloy design method has been proved to be an efficient way in designing
the lower elastic modulus titanium alloys. With the increase of
and
in Ti-Nb-Zr
ternary alloys, the lattice parameters increase monotonously while the elastic modulus
decreases monotonously with the single bcc phase structure. As the
and
increase up further to a higher value, the phase structure of the alloy changes from bcc
phase to hcp phase, resulting in a rebound of elastic modulus increment. The lattice
parameter and phase structure both have significant influences on the elastic modulus of
titanium alloys.
Acknowledgments
This work was supported by the Nature Science Foundation of China (Project No.
50571017). Support from State Key Lab of Advanced Metals and Materials is also
acknowledged.
References
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244(2005).
2. M. Morinaga, M. Kato, T. Kamimura, M. Fukumoto, I. Harada and K. Kubo, Titanium92,
Science and Technology, ed. F.H. Froes and I. Caplan (TMS, Warrendale, 1993).
3. J. C.Slater, Quantum theory of Molecules and Solids (McGraw Hill, New York, 1974).
4. M Abdel-Hady, K. Hinoshita, M. Morinaga, Scripta Materialia, 55, 477(2006).
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Materialia, 57, 1000(2007).
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