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Materials and Design 53 (2014) 8–12

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Materials and Design


journal homepage: www.elsevier.com/locate/matdes

Novel b-type Zr–Mo–Ti alloys for biological hard tissue replacements


Li Nie, Yongzhong Zhan ⇑, Hao Liu, Chenghuang Tang
College of Materials Science and Engineering, Guangxi University, Nanning, Guangxi 530004, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In order to develop new biomaterials for hard tissue replacements, Zr–12Mo–xTi (x = 0, 3, 7 and 11, in
Received 24 April 2013 at.%) alloys with required properties have been designed and prepared using vacuum arc melting method
Accepted 2 July 2013 for the first time. Phase analysis and microstructural observation shows that all the as-cast samples con-
Available online 12 July 2013
sist of equiaxed b-Zr phase. Variations of lattice constants, volume and density of the Zr–12Mo–xTi alloys
as a function of Ti content have been discussed. With the increase of Ti content, the microstructure is
Keywords: refined. The solid solution effect of the b-phase stabilization elements (i.e. Mo and Ti) predominantly
Zirconium alloys
determines the mechanical properties. These b-type Zr–12Mo–xTi alloys exhibit high compressive
Biomaterials
Microstructure
strength (1469–1584 MPa), high yield strength (1175–1375 MPa), high elastic energy (21–28 MJ/m3)
Mechanical properties and low Young’s modulus (32–35 GPa), together with plastic strain (11–25%). As the Zr–12Mo–xTi alloys
are based on biocompatible elements, this good combination of biomechanical characteristics makes
them potential biomedical materials for hard tissue replacements.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction make up the shortcoming of Ti-based biomaterials, it is very


necessary to explore some other biological materials.
During the past decades, the biological hard tissue replacement As an alloying element, Zr is often added into Ti alloys to
materials have been well studied and developed. Some conditions improve their mechanical properties. It is well known that the bio-
should be met for the practical applications of these materials. First logical behavior of Zr is similar to Ti, so it is favorable non-toxic
of all, implant materials must possess excellent biocompatibility metal with good biocompatibility. Zr and its alloys are also known
without adverse reactions. In addition, it must have a good combi- as excellent bioactive metallic biomaterials because they can form
nation of excellent corrosion resistance in body fluid, high mechan- a bone-like apatite layer on their surfaces in the living body. Addi-
ical strength and fatigue resistance. Moreover, in order to transfer tionally, Zr exhibits high mechanical strength, high fracture tough-
adequate mechanical stress to the surrounding bones, low elastic ness and good corrosion resistance, so it can act as structural
modulus (close to that of a human bone (15–30 GPa)) and good material. As a result, Zr alloys may be ideal materials developed
wear resistance are required [1,2]. In recent years, a lot of works for the biological hard tissue replacements. However, up to now
have been done to obtain the low elastic modulus biological hard reports on the application of Zr alloys in biological hard tissue
tissue replacement materials [3–6]. replacements are still very rare. The microstructure and magnetic
The Ti–6Al–4V alloy was one of the first titanium biomaterial susceptibility of as-cast Zr–Mo alloys have been investigated and
introduced in implantable components and devices. However, the it is found that these alloys are useful for medical devices applied
modulus of Ti–6Al–4V usually reaches about 110 MPa, which is under the magnetic resonance imaging [10]. In addition, the Zr–Si
substantially higher than that of natural human bone (10– biomaterials with high strength and low elastic modulus (Young’s
30 MPa) [7]. It should be pointed out that the human body may modulus in the range of 25.08–29.63 GPa) were developed recently
be seriously damaged when the implant materials do not match [2]. It would be of academic interest to design and develop new
with the human bone. To solve this problem, lots of new biomed- Zr-based biomaterials for hard tissue replacements using the bio-
ical Ti alloys have been developed, for instance, the newly devel- compatible elements like Mo and Ti.
oped single b-Ti phase type alloys can effectively reduce the In this paper, the Zr–12Mo–xTi alloys with Ti content of
elastic modulus [8,9]. However, it is still a long way to develop 0–11.0 at.% are designed. Phase composition, microstructure and
the suitable biological hard tissue replacement materials which mechanical properties like compressive stress, Young’s modulus
have elastic modulus close to human bone. Therefore, in order to and elastic energy in as-cast conditions, have been investigated.
The purpose is to develop potential biomedical materials for hard
⇑ Corresponding author. Tel.: +86 771 3272311; fax: +86 771 3233530. tissue replacements like artificial knee joints, artificial hip bones
E-mail addresses: zyzmatres@gxu.edu.cn, zyzmatres@aliyun.com (Y. Zhan). and skulls, etc.

0261-3069/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.07.008
L. Nie et al. / Materials and Design 53 (2014) 8–12 9

2. Experimental procedure Zr–Nb and the Zr–Mo binary phase diagrams [13,16], it is found
that Nb and Mo form infinite and limited solid solution in Zr,
The Zr–12Mo–xTi alloys with nominal composition (in atomic respectively. In this work, we mainly want to make use of the solid
fraction) of Zr–12Mo, Zr–12Mo–3Ti, Zr–12Mo–7Ti and Zr–12Mo– solution strengthening of alloying elements to improve the
11Ti have been melted in the WK-II type non-consumable vacuum strength of the Zr alloys. According to the mechanism of solid solu-
arc melting furnace. The contents of the components are chosen tion strengthening, distortion energy caused by solid solution
mainly based on the information of phase diagrams and thermody- atoms can hinder the movement of dislocations and increase
namics [11–13]. The raw materials were sponge zirconium, molyb- strength and hardness. The larger the lattice distortion is, the more
denum and sponge titanium with purity all higher than 99.9%. In significant the strengthening effect is. Mo forms limited solid solu-
order to make the samples react and mix adequately in the molten tion in b-Zr, so it leads to greater lattice distortion as well as higher
state, the highest melting temperature was higher than 3000 °C by strengthening effect than that of Nb. Accordingly, we select Mo as
setting the current intensity. The reaction and melting time for b-Zr-stabilizing elements in the alloy system. However, an exces-
each sample was kept for 80 s. The molten samples were cooled sive amount of solution elements may seriously degrade the
down directly in the water-cooled copper melting pots (by running mechanical properties of alloys, so a component percentage of
water at room-temperature) with cooling time of about 500 s. In 12 at.% is selected. This composition is slightly higher than the
order to ensure the chemical homogeneity of each sample, all eutectoid point of the reaction components and thus is conducive
ingots were turned over and remelted six times. to formation of the metastable b-Zr alloys. In order to further
The samples for optical and secondary electron microscopy improve the mechanical properties of Zr–12Mo-based alloys, Ti
were cut by electric discharge machining (EDM) from the ingots. was chosen as the third alloying elements. According to the Zr–Ti
The samples for metallographic observations were mounted and binary phase diagram [12], these two elements can form an infinite
mechanically polished with SiC paper and Al2O3 particles with solid solution and prone to form the metastable b-Zr alloys at room
water. The polished sample were etched in an erodent with temperature. To study the influence of Ti on the mechanical prop-
composition of HF (aqueous solution): HNO3 (aqueous solution): erties, the Ti content is selected in the range of 0–11 at.%.
water = 1:2:6 (ratio by volume). The weight percents of HF aque-
ous solution and HNO3 aqueous solution were 40% and 65%, 3.2. Phase identification and microstructure of the Zr–12Mo–xTi alloys
respectively.
Phase identification was carried out via X-ray diffraction (XRD) Fig. 1 shows the XRD patterns of the as-cast Zr–12Mo–xTi alloys
using Rigaku D/Max 2500V diffractometer with Cu Ka radiation (in at.%), it is found that the solid state phase of all samples at room
and graphite monochromator operated at 40 kV and 200 mA. The temperature is b-type Zr. It is noted that Ti, Zr and Mo have the
microstructures were determined from DMM-660 type optical same structure-type, space group and similar crystal lattice, which
microscopy and Hitachi S-3400N scanning electron microscope means that they may completely dissolved with each other and
(SEM) equipped with energy dispersive (EDX) analysis. The dimen- form the metastable b phase at high temperatures [17]. However,
sion of the compression specimen was of 5 mm  5 mm  10 mm. the solid state phase at room temperature is closely related to cool-
Three samples were tested for each alloy to get the average values. ing rate after the alloys have solidified from high-temperature
Compression test was conducted using Instron 8801 axial servohy- liquid [18]. As analyzed above, Ti and Zr can completely dissolve
draulic dynamic testing system according to ASTM: E9-09. with each other at any temperature [12]. In addition, Mo belongs
to 4d transition metallic element and can effectively stabilize the
b-Zr phase. In this work, all the alloys were produced in the
3. Results and discussion water-cooled copper crucible using arc melting. The cooling rate
may be so fast for the small button samples that the b-type Zr
3.1. Component selection principle has no sufficient time for phase transition. Moreover, due to the
similarity of the crystal structure and the lattice parameter, Zr
In this work, we have two targets for the design of these biolog- and Mo elements may completely dissolve in each other and then
ical hard tissue replacement materials. Firstly, the elastic modulus results in ideal undercooling. This helps to form the metastable b
of the material should be effectively reduced so that the elastic phase at high temperatures. Hence, the b-Zr is kept at room
modulus can substantially comply with the elastic modulus of temperature in the as-cast alloys.
the human skeleton (10–30 GPa). This may thereby reduce the Variations of lattice constants, volume and density of Zr–
effects of stress shielding between implant material and human 12Mo–xTi alloys as a function of the Ti content have been
bone, and then improve security in the service process. Secondly,
strength of the biological material should be improved to with-
stand external force, which may prolong the service life of the
implant material. As hard tissue replacements are mainly affected
by compression stress, the principal mechanical test is conducted
on compressive properties.
In order to effectively reduce the elastic modulus of the Zr
alloys, b-Zr phase should be obtained at room temperature. As
we know, Zr has two types of crystal structure, i.e. a-Zr (close-
packed hexagonal structure) and b-Zr (body-centered cubic struc-
ture). The elastic modulus of the b-Zr (about 60 GPa) is much lower
than that of the a-Zr (about 100 GPa) [14,15]. However, as the b-Zr
is a high-temperature phase, b-Zr stabilizing elements like Mo, Nb,
Ta, etc. should be used to decrease the phase change transition
temperature of b-Zr ? a-Zr, so as to obtain b-Zr phase at room
temperature. As a foundation for the future practical application,
this experiment takes into account the cost of raw materials. Thus
the expensive Ta element is not considered here. According to the Fig. 1. XRD patterns of the as-cast Zr–12Mo–xTi (x = 0, 3, 7 and 11) alloys.
10 L. Nie et al. / Materials and Design 53 (2014) 8–12

Table 1
Lattice constants, volume and density of the b-type Zr–12Mo–xTi (x = 0, 3, 7 and 11)
biomedical alloys.

Alloys a (Å) v (Å3) q (g/cm3) Reference


Zr–12Mo 3.5403 44.37 6.827 This work
Zr–12Mo–3Ti 3.5392 44.33 6.834 This work
Zr–12Mo–7Ti 3.5200 43.62 6.946 This work
Zr–12Mo–11Ti 3.5014 42.93 6.985 This work
Zr 3.5680 45.42 6.670 [19]

discussed by using the software Jade 5.5, as shown in Table 1. The


b-Zr has cubic structure with space group Im-3m (No. 229). There
are two Zr atoms occupying the 2a Wyckoff site (0, 0, 0) of each
unit cell [19]. It is noted that the lattice constants and volume of
the unit cell of Zr–12Mo are a little lower than that of pure b-Zr.
As the radius of Mo (2.01 Å) is lower than that of pure b-Zr
(2.16 Å), the lattice constants and the volume of the unit cell of Fig. 3. Room-temperature compressive stress–strain curves of the b-type Zr–
Zr–12Mo are a little lower than pure b-Zr. In addition, the radius 12Mo–xTi (x = 0, 3, 7 and 11) biomedical alloys.

lies between that of Mo and Zr, which means that Mo addition


can only form substitution solid solution in the Zr matrix. There-
fore, even if the Mo content is up to 12 at.%, the lattice constants Table 2
of Zr–12Mo is very close to pure b-Zr. According to Table 1, it is Mechanical properties of the b-type Zr–12Mo–xTi (x = 0, 3, 7 and 11) biomedical
found that the lattice constant of Zr–12Mo–xTi decreases with the alloys.
increase of Ti content, which is due to the fact that the radius of Alloys Young’s Compressive Yield Elastic Plastic
Ti (2.00 Å) is lower than that of Zr and Mo. Moreover, with the modulus strength strength energy strain
increase of Ti content, the density of Zr alloys increases. It should (GPa) (MPa) (MPa) (MJ/m3) (%)
be related to the relative atomic weight of solution atoms and Zr–12Mo 33.075 1542 1200 21.77 19.64
unit cell volume. As the relative atomic weight of Ti (47.87) is Zr–12Mo–3Ti 33.160 1582 1211 22.11 24.74
Zr–12Mo–7Ti 33.525 1504 1235 22.74 19.44
much lower than that of Zr (91.22), the density of Zr–12Mo–xTi
Zr–12Mo–11Ti 34.130 1485 1363 27.21 12.40
should decrease if the volume change is not considered. However,
the densities of Zr alloys increase with the increasing of Ti con-
tent, which indicates that the densities of these alloys are primar-
ily determined by the change of volume. Therefore, it can be can be clearly observed. The grain boundaries which form the large
concluded that the addition of Ti in Zr–12Mo alloys cannot make grains of b phase are seen clearly. It was observed that the grains of
them lighter. b-Zr alloy became smaller and the microstructure was refined with
The typical secondary electron micrographs of the b-type the increase of Ti content. The reason may be the fact that Ti ele-
Zr–12Mo–xTi biomedical alloys are displayed in Fig. 2. Due to the ment restrains the precipitation of Mo from the grain boundary
solubility of alloying elements in Zr, the equiaxed b crystal grain and makes the grain boundary closer.

Fig. 2. Typical secondary electron micrographs of the b-type Zr–12Mo–xTi biomedical alloys: (a) x = 0, (b) x = 3, (c) x = 7 and (d) x = 11.
L. Nie et al. / Materials and Design 53 (2014) 8–12 11

3.3. Mechanical properties

Fig. 3 shows the room-temperature compressive stress–strain


curves of the b-type Zr–12Mo–xTi (x = 0, 3, 7 and 11) biomedical
alloys. It is found that the alloying element Ti has an important im-
pact on the mechanical properties of the material. It can be inferred
that both the compressive strength and the plastic strain of the
Zr–12Mo–xTi alloys are sensitively (but nonlinearly) affected by
the Ti content. Table 2 lists the values of Young’s modulus, com-
pressive strength, yield strength, elastic energy and plastic strain
for the Zr–12Mo–xTi (x = 0, 3, 7 and 11) biomedical alloys. When
x is 3.0, the material has the highest compressive strength
(1582 GPa) and plastic strain (24.74%). However, when x is higher
than 7.0, the compressive strength and the plastic strain of the
alloys decrease very rapidly. The above results can be analyzed
based on both grain refinement and solid-solution strengthening
Fig. 4. Young’s modulus and yield strength of the b-type Zr–12Mo–xTi (x = 0, 3, 7
and 11) biomedical alloys as a function of Ti content. effects. As we know, the smaller the grain size is, the better the
strength and ductility of the metallic material are at room temper-
ature. Although solid solution strengthening can effectively im-
prove the strength of the metallic materials, it may also decrease
the plasticity. It has been confirmed above that addition of Ti ele-
ment results in the grain refinement of Zr alloys. The Zr–12Mo–3Ti
has the highest compressive strength and plastic strain, which
indicates that the mechanical properties are dominated by grain
size. When x is higher than 7.0, due to the increase of solution
atoms, the mechanical properties is mainly determined by solid
solution strengthening. It is known that metallic materials with
good ductility may exhibit significant hardening effect under com-
pression. Therefore, the Zr–12Mo–3Ti has the highest compressive
strength.
According to Table 2 and Fig. 4, Young’s modulus is nonlinearly
improved by increasing the amount of Ti element. It is noted that
the Young’s modulus ranges from 32 to 35 GPa, which is very close
to the human body (15–30 GPa). Therefore, the present material
system is expected to avoid the damage caused by the mismatch
of mechanical properties between the implant material and the
Fig. 5. Illustration of elastic energy in a stress–strain plot. human bone. In addition, the yield strength also increases nonlin-

Fig. 6. SEM images of the fractured surfaces of the compressively-tested samples: (a) Zr–12Mo, (b) Zr–12Mo–3Ti, (c) Zr–12Mo–7Ti and (d) Zr–12Mo–11Ti.
12 L. Nie et al. / Materials and Design 53 (2014) 8–12

early with the increasing of Ti content, as shown in Fig. 4. Although (2) The mechanical properties of Zr–12Mo–xTi have been
the yield strength is affected both by solid solution strengthening analyzed. It is found that these Zr–12Mo–xTi alloys exhibit high
and grain refinement, the first one is dominant for the Zr–12Mo– compressive strength (1469–1584 MPa), high yield stress (1175–
xTi materials. As shown in Table 2, the highest yield strength 1375 MPa), high elastic energy (21–28 MJ/m3) and low Young’s
reaches 1363 MPa, which is higher than the vast majority of bio- modulus (32–35 GPa), together with plastic strain of 11–25%. This
medical titanium alloys [3]. Even the lowest yield strength of our good combination of mechanical characteristics makes them
designed material system is up to 1200 MPa. potential biomedical materials for biological hard tissue
replacement.
3.4. Elasticity of the b-type Zr–12Mo–xTi biomaterials (3) Finally, the fractured surfaces of Zr–12Mo–xTi (x = 0, 3, 7 and
11) biomedical alloys have been analyzed. The fracture modes of
Combination of high strength and low elastic modulus is Zr–12Mo–xTi alloys are a combination of cleavage fracture and
required for the metallic implant materials. Fig. 5 shows that the ductile fracture. With the increase of Ti content, the cleavage frac-
stress–strain curve in the elastic stage makes up a triangle. The ture gradually becomes the dominant factor.
mathematic expression of the elastic energy can be expressed as:

1 r2 Acknowledgements
de ¼ ee ry ¼ y ð1Þ
2 2E
This research work is supported by the National Natural Science
where de is the elastic energy, ee is the elastic strain, ry is the yield
Foundation of China (51161002) and the Program for New Century
strength and E is the Young’s modulus [20]. According to Eq. (1), the
Excellent Talents in University of China (NCET-12-0650).
elastic energies of the b-type Zr–12Mo–xTi (x = 0, 3, 7 and 11) alloys
are calculated and listed in Table 2. It can be seen that the elastic
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