journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

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Short Communication

-Type ZrNbTi biomedical materials with high

plasticity and low modulus for hard
tissue replacements
Li Nie, Yongzhong Zhann, Tong Hu, Xiaoxian Chen, Chenghui Wang
College of Materials Science and Engineering, Guangxi University, Nanning, Guangxi 530004, PR China

art i cle i nfo

ab st rac t

Article history:

In order to develop new biomedical materials for hard tissue replacements, Zr20NbxTi

Received 13 July 2013

(x 0, 3, 7, 11 and 15) alloys with required properties were designed and prepared by using

Accepted 15 August 2013

the vacuum arc melting method for the rst time. Phase analysis and microstructural

Available online 28 August 2013

observation showed that all the as cast samples consisted of equiaxed -Zr phase. The

Keywords:

mechanical properties and fracture behaviors of the Zr20NbxTi alloys have been

ZrNbTi alloys

analyzed. It is found that these alloys exhibit high plasticity, moderate compressive

-Type

strength (10441325 MPa) and yield stress (8541080 MPa), high elastic energy (1220 MJ/m3)

Biomedical materials

and low Young's modulus (2831 GPa). This good combination of mechanical properties

Mechanical behavior

makes them potential biomedical materials for hard tissue replacement.

1.

Introduction

Currently, development of biological hard tissue replacements (HTR) has attracted increasing attention. However,
only part of the investigated materials may be applied for
HTR, as a number of conditions should be satised. Firstly,
the implant materials must possess excellent biocompatibility without adverse reaction with human body. Secondly, it
should have excellent corrosion resistance in body uid, high
mechanical strength and fatigue resistance. Finally, good
wear resistance and low elastic modulus (close to that of a
human bone (1530 GPa)) are required, in order to transfer
adequate mechanical stress to the surrounding bones (Guo
et al., 2010; Li et al., 2011).
Ti6Al4V alloy was one of the earliest Ti-based biomaterials introduced in implantable components and devices.
However, the modulus of Ti6Al4V reaches about 110 GPa,
n

Corresponding author. Tel.: 86 771 3272311; fax: 86 771 3233530.

E-mail address: zyzmatres@yahoo.com.cn (Y. Zhan).

1751-6161/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jmbbm.2013.08.019

& 2013 Elsevier Ltd. All rights reserved.

which is substantially higher than that of natural human

bone (1030 GPa) (Niinomi, 1998). As a result, the human body
may be seriously damaged under external applied load due to
the elastic mismatch. Therefore, biomaterials with low elastic
modulus are attracting the attention of researchers. It is
found that new type biomedical Ti alloys with single -Ti
phase can effectively reduce the elastic modulus to be about
6080 GPa (Nag et al., 2007; Niinomi, 2004), which is closer to
the human bone. However, to develop suitable HTR materials,
the elastic modulus should be further reduced without
deterioration of the other properties. Consequently, development of the other metal-based biocompatible materials is an
important solution.
Zr is an important alloying element for Ti-based alloys to
improve mechanical properties. More importantly, similar to
Ti, Zr is a favorable non-toxic metal with good biocompatibility with organism. Zr and its alloys are known as excellent

journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

bioactive metallic materials because a bone-like apatite layer

may be formed on their surfaces in living body. In addition, Zr
alloys exhibit high mechanical strength, fracture toughness
and corrosion resistance (Inoue, 2000; Niinomi, 2003; Okazaki
et al., 1998; Wen et al., 2006), therefore they are potential
biomaterials for hard tissue replacements. However, up to
now very few report can be found on the Zr-based biomedical
materials. Microstructure and magnetic susceptibility of ascast ZrMo alloy have been investigated, and it was reported
that the alloys are useful for medical devices applied under
magnetic resonance imaging (Suyalatu et al., 2010). Li et al.
(2011) have developed ZrSi biomaterials with high strength
and low elastic modulus (25.0829.63 GPa), which satises
well the requirements of HTR. ZrNb alloys were previously
used as nuclear materials, thus the investigations were
mainly focused on microstructural stability and corrosion
behaviors under various conditions (Arima et al., 2005;
Aurelio et al., 2001; Benites et al., 2000; Dey et al., 1995;
Jeong et al., 2002; Kim et al., 2008). However, as biomedical
materials, the ZrNb alloys have gradually attracted the
attention of some researchers (Kondo et al., 2011; Akahori
et al., 2011a, 2011b). For instance, recently the mechanical
properties and biocompatibilities of the ZrNb alloys have
been experimentally studied (Akahori et al., 2011a, 2011b).
In this paper, the Zr20NbxTi alloys are designed, with
Ti content in the range from 0 to 15.0 at%. The object is to
develop potential biomedical materials with appropriate
mechanical properties (i.e. low Young's modulus, favorable
ductility, and moderate strength) for hard tissue replacements. The phase composition, microstructure and mechanical properties including compressive stress, Young's
modulus and elastic energy of the as-cast Zr20NbxTi (x
0, 3, 7, 11 and 15) alloys have been investigated.

2.

Experimental procedure

The Zr20NbxTi alloys with nominal composition (in atomic

fraction) of Zr20Nb, Zr20Nb3Ti, Zr20Nb7Ti, Zr20Nb11Ti
and Zr20Nb15Ti have been melted by using the WK-II type
non-consumable vacuum arc melting furnace. The raw
materials were pure sponge zirconium, pure niobium and
pure sponge titanium with purity all higher than 99.9 wt%. In
order to ensure adequate mixing and reaction of the samples
in molten state, the melting temperature was controlled to be
as high as 2500 1C by setting the current intensity. The
reaction and melting time for each sample was kept for
80 s. The molten samples were then cooled down directly in
the water-cooled copper melting pots (by running water at
room-temperature) with cooling time is about 500 s. In order
to ensure chemical homogeneity of each sample, all the
ingots was turned over and remelted for six times.
Samples for optical and secondary electron microscopy
were cut by electric discharge machining (EDM) from the
ingots. They were mounted and then mechanically polished
with SiC paper and Al2O3 particles with water. The polished
samples were etched in an erodent with composition of
HF (aqueous solution): HNO3 (aqueous solution): water1:2:6
(ratio by volume). The weight percents of the HF aqueous

solution and the HNO3 aqueous solution were 40% and 65%,
respectively.
Phases identication were carried out via X-ray diffraction
(XRD) using Rigaku D/Max 2500 V diffractometer with Cu Ka
radiation and graphite monochromator operated at 40 kV and
200 mA. The microstructures were determined from DMM660 type optical microscopy and Hitachi S-3400N scanning
electron microscope (SEM) equipped with energy dispersive
(EDX) analysis. The dimensions of the compression specimen
were 5 mm  5 mm  10 mm. Three samples were tested for
each alloy to get the average values. Compression test was
conducted at room temperature in air at an initial strain rate
of 1 mm/min by using the Instron 8801 axial servohydraulic
dynamic testing system, to determine the mechanical properties including ultimate compressive strength, fracture
strain and Young's modulus etc.

3.

Results and discussion

3.1.

Component selection principle

In this work, there are two objects for the design of these
biological HTR materials. Firstly, the elastic modulus should
be effectively reduced to comply with that of the human
bones (1030 GPa). This measure can reduce the effects of
stress shielding between the implant material and bones.
Secondly, the strengths (including the yield strength and the
compressive strength) of the HTR material should be moderately improve to withstand external force. This measure
helps to prolong the working life of the HTR components. It
should be pointed out that as the hard tissue is mainly
affected by compression stress, so the compressive properties
are principally considered in this work. At the same time,
excellent ductility is also required because it is important for
processing the HTR materials into components with various
shapes.
It is known that for the two crystal structures of Zr (i.e.
close-packed hexagonal -Zr and body-centered cubic -Zr),
the elastic modulus of the -Zr (about 60 GPa) is much lower
than that of the -Zr (about 100 GPa) (Cai et al., 2009; Kondo
et al., 2011). As a result, in order to effectively reduce the
elastic modulus of the zirconium alloy, -Zr should be
obtained at room temperature. However, since the -Zr
belongs to high-temperature phase, the so-called phase
stabilizing elements like Mo, Nb, Ta, etc. should be added in
the alloys to effectively decrease the -Zr and -Zr phase
change transition temperature. Considering the future practical applications, the expensive raw material Ta is excluded.
In this work, we mainly want to improve the strength of the
Zr alloy through the solid solution strengthening of alloying
elements. For this strengthening mechanism, the distortion
energy caused by lattice distortion can hinder the movement
of dislocations and thus improve the strength. Larger lattice
distortion results in more signicant strengthening effect, but
also decreases the plasticity. According to the ZrNb and the
ZrMo binary phase diagrams (Abriata and Bolcich, 1982;
Zinkevich and Mattern, 2002), the elements Nb and Mo can
form innite and limited solid solutions in Zr, respectively.
Therefore, Nb element may result in smaller lattice distortion

journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

and obtain a good combination of ductility and strength, as

compared with Mo. Accordingly, we select Nb as the major Zr-stabilizing element for the designed alloys. In order to
decrease the - phase transition temperature as far as
possible and avoid the generation of coarse grains, the
content of Nb is designed to be 20 at% (which is slightly
higher than the segregation reaction transition component
point, but slightly lower than that of the eutectic reaction
(Abriata and Bolcich, 1982)). To further improve the mechanical properties, Ti is chosen as the third alloying element for
the ZrNb alloys. According to the ZrTi binary phase diagram
(Murray, 1981), these two elements can form an innite solid
solution. Ti is conducive to the formation of metastable -Zr
alloys at room temperature. Ti content is designed to be in
the range from 0 to 15 at% to investigate the inuence of Ti
content on the mechanical properties of the Zr20Nb alloy.

3.2.

Phase identication and microstructure

XRD patterns of the as-cast Zr20NbxTi (x 0, 3, 7, 11 and 15)

alloys are shown in Fig. 1. It is clearly indicated that the solid
state phase composition of all the samples is -type Zr. As
Ti and Zr can dissolve completely with each other at any
temperature (Murray, 1981), the effect of Ti element on the
phase composition of Zr alloys should be weak. Nb belongs to
4d transition metallic element, which is effective to stabilize
the -Zr phase. In addition, it is noted that Zr and Nb can
completely dissolve with each other in the phase region
(Abriata and Bolcich, 1982). The room-temperature phase
composition at is closely related to the cooling rate after
the alloys have been solidied from high-temperature liquid
(Li et al., 2012). In this work, all the alloys were produced in
the water-cooled copper crucible by using arc melting. The
cooling rate may be too fast for the small button samples to
reach equilibrium state. In other words there is no sufcient
time for the solid phase transition (-Zr--Zr). Moreover, due
to the similarity of the crystal structure and lattice parameter
between Zr and Nb elements, they may completely dissolve
in each other and then result in ideal undercooling. This
helps to form the metastable phase at high temperatures.
Hence, the high-temperature phase -Zr is kept at roomtemperature in the as-cast samples. In addition, it is found

Fig. 1 XRD patterns of the as-cast Zr20NbxTi (x 0, 3, 7, 11

and 15) alloys.

that with the increase of Ti content, the intensities of XRD

peaks change accordingly, which indicates that the crystalline process has been affected.
Typical secondary electron micrographs of the as-cast Zr
20NbxTi (x 0, 3, 7, 11 and 15) biomedical alloys are displayed in Fig. 2. As both Nb and Ti can dissolve in the Zr
matrix, equiaxed -Zr crystal grain can be clearly observed.
The grain boundaries of the -Zr crystal grain are also seen
clearly. In addition, compared with the Zr20Nb sample,
addition of Ti element makes the grain boundary closer and
renes the microstructure. This may be due to the fact that Ti
element restrains the precipitation of Nb from the grain
boundary and then reduces the thickness of grain boundary.

3.3.

Mechanical properties

Fig. 3 shows the room-temperature compressive stressstrain

curves of the -type Zr20NbxTi (x 0, 3, 7, 11 and 15)
biomedical alloys. It is found that Ti element has an important impact on the mechanical properties. It is noted that the
slope of elastic stage changes slightly with the increasing of
Ti content. This indicates that Ti element has little effect on
the stiffness of Zr20Nb alloy. As we know, the stressstrain
curves can describe the hardening growth trend in the
process of plastic deformation. According to Fig. 3, it is found
that all the samples do not exhibit signicant hardening
effect with the increase of pressure. This means that the
Zr20NbxTi (x 0, 3, 7, 11 and 15) alloys are suitable to be
processed into different shapes. Table 1 lists the values of
Young's modulus, compressive strength, yield strength, elastic energy and plastic strain of these biomedical alloys. It is
found that all the samples exhibit high (and also close) plastic
strains, which should be related to the mechanisms of
various solid solution types. Since both Nb and Ti can
completely dissolved in the -Zr matrix, they may limitedly
enhance the strength and maintain relatively high ductility.
In this work, the maximum compression distance was set to
be 4 mm. However, all the samples were not crushed in this
compression distance. Compression cracks of the tested
samples are shown in Fig. 4. It is observed that the angles
between the compression direction and cracks are about 451.
According to the width of the cracks, it is inferred that the
plasticity is relatively good Ti content ranges from 7% to 11%.
In this work, low Young's modulus is a highlight for the
Zr20NbxTi system. As listed in Table 1, the Young's
modulus ranges from 28 to 31 GPa, which meets the requirement of HTR for human body (1530 GPa) well. Therefore, the
present material system is expected to solve the problem
caused by the mismatch of elastic properties between the
implant materials and human bones. It should be pointed out
that the solid solution strengthening is signicantly affected
by Ti element. As the Young's modulus is dened to be the
ratio of the normal stress and strain in the elastic deformation stage, both the deformation resistance and the Young's
modulus are increased due to more Ti addition. Accordingly,
the compressive strength and the yield strength increase
with increasing Ti content. The Zr20Nb15Ti sample has the
highest compressive strength (1307718 MPa) and yield
strength (1071710 MPa), which could be considered as relatively high values for the biological hard tissue substitute

journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

Fig. 2 Typical secondary electron micrographs of the -type Zr20NbxTi biomedical alloys: (a) x 0; (b) x 3; (c) x 7; (d) x 11;
(e) x 15.

designed alloys may be suitable for pressure process to make

biomedical HTR component with different shapes. Though
the mechanical properties are affected by various factors like
solid solution and microstructural renement, the former
should be the predominant one.

3.4.

Fig. 3 Room-temperature compressive stressstrain curves

of the -type Zr20NbxTi (x 0, 3, 7, 11 and 15) biomedical
alloys.

materials (Niinomi, 1998). For the present Zr20NbxTi alloys,

when Ti content ranges from 7 at% to 11 at%, good combination of mechanical properties (favorable plastic strain, moderate compressive strength and yield strength, low elastic
modulus) is obtained. These properties also ensure that the

Elasticity

The hard tissue replacement components usually work in

elastic deformation conditions. In the deformation process,
the work done by the external force may store in the solid as
energy. When the external force decreases, the deformation
of solid also decreases, and then the elastic energy may be
released. Therefore, investigation of the elastic energy is
important for understanding the mechanical behaviors of
biological HTR materials. Fig. 5 shows that the elastic strain,
the yield strength and the stressstrain curve in the elastic
stage make up a triangle. The mathematic expression of the
elastic energy can be expressed as
e

s2y
1
e sy
2
2E

journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

Table 1 The mechanical properties of the -type Zr20NbxTi (x 0, 3, 7, 11 and 15) biomedical alloys.
Alloys
Zr20Nb
Zr20Nb3Ti
Zr20Nb7Ti
Zr20Nb
11Ti
Zr20Nb
15Ti

Young's modulus
(GPa)

Compressive strength
(MPa)

28.97570.085
29.68570.465
29.02070.94

104672
111079
1145715

29.30570.045
29.91570.535

Yield strength
(MPa)

Elastic energy (MJ/

m3)

Plastic strain
(%)

85773
89077
91075

12.7370.01
13.7070.03
13.6570.01

37.8470.07
37.6270.13
38.0270.06

1204719

104377

18.5670.54

38.1070.02

1307718

1071710

19.1570.08

37.6970.01

Fig. 4 SEM images of the crack of the compressively tested samples: (a) Zr20Nb, (b) Zr20Nb3Ti, (c) Zr20Nb7Ti, (d) Zr
20Nb11Ti, and (e) Zr20Nb15Ti.

where e is the elastic energy, e is the elastic strain, sy is the

yield strength and E is Young's modulus (Zhan et al., 2012).
According to Eq. (1), the elastic energies of the -type
Zr20NbxTi (x 0, 3, 7, 11 and 15) alloys are calculated and
listed in Table 1. It is indicated that the elastic energy is
sensitive with the variation of Ti content. The elastic energy
of the Zr20NbxTi alloy ranges from 12 MJ/m3 to 20 MJ/m3,
which is higher than most of the reported bio-Ti-base alloys
(i.e. 15 MJ/m3) (Niinomi, 1998; Zhan et al., 2012). This result

means that the present material system can withstand

greater elastic deformation.

4.

Conclusions

In order to develop novel biomedical HTR materials with

required properties, the -type Zr20NbxTi (x 0, 3, 7, 11 and
15) alloys were designed and fabricated for the rst time. The
effects of Ti element on the microstructure and mechanical

journal of the mechanical behavior of biomedical materials 29 (2014) 1 6

Fig. 5 Illustration of elastic energy in a stressstrain plot.

properties of the binary Zr20Nb alloy were investigated. The

following results are got:
(1) All the as cast Zr20NbxTi samples contain only one
phase (-Zr). The size of the equiaxed -Zr grains is greatly
affected by the Ti content. The grain size and grain
boundary are rened with more Ti addition.
(2) The Zr20NbxTi alloys exhibit a good combination of
mechanical properties including nice plasticity, moderate
compressive strength (10441325 MPa) and yield stress
(8541080 MPa), high elastic energy (1220 MJ/m3) and
low Young's modulus (2831 GPa). As it meets most of
the required properties for hard tissue replacements,
these novel biomaterials are considered to be potential
candidate for future applications.

Acknowledgments
This research work is jointly supported by the National
Natural Science Foundation of China (51161002) and the
Program for New Century Excellent Talents in University of
China (NCET-12-0650).

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