journal of the mechanical behavior of biomedical materials 60 (2016) 68 77

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Research Paper

Mechanical and electrochemical characterisation of

new TiMoNbZr alloys for biomedical applications

Paul S. Nnamchia,b,n, C.S. Obayib, Iain Todda, M.W. Rainfortha

a
Department of Materials Science and Engineering, University of Shefeld, Mapping St, Shefeld S1 3JD, United Kingdom
b
Department of Metallurgical and Materials Engineering, University of Nigeria, post code 410001, Nsukka, Enugu state,
Nigeria

ar t ic l e in f o abs tra ct

Article history:
Received 1 October 2015
Received in revised form
15 December 2015
Accepted 18 December 2015
Available online 28 December 2015
The development and characterisation of new metallic biomaterials that contain non-toxic
and non-allergic elements but possess low elastic modulus and low biodegradation rates,
has become a topic of serious investigation in orthopaedic implant application. The
lowering of elastic modulus and improving of corrosion resistance can be achieved by
specic chemical alloying and super-elasticity effects, associated with a stress-induced
phase transformation from the BCC metastable beta phase to the orthorhombic

Keywords: martensite. Using this framework, this paper focuses on the effect of Nb and/or Zr

Titanium alloys micro-additions on the elastic modulus/yield strength balance and discusses microstruc-

Metals and alloys ture, and the mechanical and electrochemical behaviour of four new -Ti8MoxNbxZr

Electrochemical characterisation (x25) alloys, using tensile tests, X-ray diffraction, SEM characterisation, ultrasound

Biomedical application technique and potentiodynamic polarisation methods. The results reveal that the alloys

Non-toxic element exhibit a pronounced microstructural sensitivity response, with alloying elements and

low elastic modulus excellent agreement between -stability and high mechanical strength, with increasing Nb
additions. Although all the alloys possess excellent corrosion resistance and low Young's
modulus, Ti8Mo4Nb2Zr alloy, which consists of 00 phases, exhibits a low Young
modulus of 35 GPa, which is lower than those of the commercial alloys already used in
biomedical implantation. The signicant corrosion resistance, nontoxicity and better
mechanical compatibility are properties pertinent to preventing stress shielding and bone
resorption in orthopaedic implant applications.
Crown Copyright & 2015 Published by Elsevier Ltd. All rights reserved.

1. Introduction standards and consequences such as an increased number of

people living with senility, who, due to degenerative diseases
Biomaterials research has attracted great attention due to such as arthritis, may need medical assistance in maintain-
increasing economic development, leading to improved living ing their mobility, increased volume of transportation in

n
Corresponding author at: Department of Metallurgical and Materials Engineering, University of Nigeria, post code 410001, Nsukka,
Enugu state, Nigeria. Tel.: 234 7064278906, 44 7928921079.
E-mail addresses: paul.nnamchi@unn.edu.ng, nnamchi.paul@gmail.com (P.S. Nnamchi).

http://dx.doi.org/10.1016/j.jmbbm.2015.12.023
1751-6161/Crown Copyright & 2015 Published by Elsevier Ltd. All rights reserved.
 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77
terms of the number of cars and associated trafc accidents,
and an increased amount of leisure time channelled into
sports that have a higher than average risk of injuries. All of
these increase the need for orthopaedic surgeries and the
consumption of biomedical materials [1]. Some biomaterials
and medical devices have been used in clinical practice over
several decades, and most perform satisfactorily, thus sig-
nicantly improving the quality of life of the recipients.
However, manufactured medical devices do have a failure
rate, owing to various problems. For example, when the
mechanical property and biodegradation rates of biomater-
ials do not match with those of the host, this can result in
stress shielding and in vivo degradation of implants, leading
to loss of functionality and integrity, and inducing local and/
or systemic effects [13]. Although tremendous efforts have
been made to solve these problems, the poor mechanical
property and biodegradation rates of biomaterials are major
aws that need to be overcome for successful biocompat-
ibility and long-term stability of implants. As a consequence,
the development and characterisation of new materials con-
taining non-toxic and non-allergic elements has become a
topic of investigation [46].
Ti alloys are one of the important implant materials used
to substitute hard tissue and form bone-implant coupling,
due to their high mechanical and fatigue resistance, low
density, high corrosion resistance, and excellent biocompat-
ibility properties [17,79]. Moreover, Ti alloys present a lower
rigidity than other implant materials such as CoCr alloys or
stainless steels [10]. Due to the lower elastic modulus exhib-
ited by the phase of titanium [1115], compared with the
values presented by the -phase, -Ti alloys are a relevant
eld of investigation. However, the phase in Ti alloys is
present at high temperature; hence, in order to stabilise this
phase at a low temperature, and obtain low elastic modulus
Ti alloys, nontoxic and non-allergic -stabilising alloying
elements are needed. From this perspective, previous studies
have shown that the most promising compromises are alloys
that present Nb, Zr, Mo, Hf and Ta (-stabiliser elements) as
alloying elements [4,5,16]. As alloying addition, Nb and Zr are
excellent well-known biocompatible elements [17,18]. The
use of Mo is still controversial [19], but recent studies have
demonstrated adequate mechanical compatibility and good
cyto-compatibility of Ti alloys containing Mo such as TiMo,
TiMoTa or TiMoZrFe [2023]. Additionally, the advantage hearth. The alloys were melted in a high purity argon atmo-
of using Mo is that it has stronger stabilising properties for
titanium alloys than Nb and Ta elements [24,25], whereas Zr
is usually regarded as a neutral element that does not
stabilise in either the or phase. However, Zr addition does
retard martensitic transformation during cooling, thereby
contributing to hardenability [26]. Antipov and Moiseev [27]
note that the addition of 6 wt% Zr (approximately 2 at%) could
produce an equivalent effect to that of 1.5% Mo.
The literature includes studies of alloys used to obtain low
elastic modulus for biomaterials application, such as Ti
13Nb13Zr [28], Ti30Zr10Nb10Ta [29], Ti4.4Ta1.9Nb [30], range for the alloys studied was designed within the range
Ti29Nb13Ta4.6Zr [31], Ti7.5Mo [10], Ti34Nb9Zr8Ta [32], where 00 exists in the TiMo alloy system (i.e. Ti-8 Mo). A
Ti16.17Nb14.65Ta3.10Zr [33] and Ti14.95Nb4.83Ta3.10Zr study of the chemical composition of the alloys was com-
[34]. In addition, some authors report a relationship between
thermo-elastic martensite 00 phase and low elastic modulus,
with Hao et al. [35] showing the inuence of ice water
69
quenching after solution treatments at different tempera-
tures and times on the formation and volume fraction of 00
phase on the Ti29Nb13Ta4.6Zr alloy. The results of this
work established elastic modulus values of the 00 phase
nearly identical to those of the phase, as well as shape
memory effects in the studied material. Li et al. [34] report a
signicant inuence of the cooling rate after solution treat-
ment on the phase obtained in Ti29Nb13Ta4.6Zr and Ti
39Nb13Ta4.6Zr alloys. The results also showed a remark-
able sensitivity to the mechanical properties, phase transfor-
mation, and elastic modulus to the phases present in these
alloys. In the case of TiMo alloy, Zhang et al. [36] conducted
different studies on phase transformations, stress release,
and the mechanical properties of different TiMo alloys using
X-ray diffraction and transmission electron microscopy. In
another paper, Zhang et al. [37] used high-resolution trans-
mission electron microscopy and insitu XRD analyses to
elucidate the compositional sensitivity of the deformation
behaviour in two TiMo-based alloys. The alloy with 8% Mo
exhibited conventional elastic/plastic behaviour in tension
which corresponds to the irreversible formation of stress-
induced 00 orthorhombic martensite. The alloy containing
10% Mo exhibited a pronounced pseudo-elastic response,
with recovery of 80% of the imposed tensile strain. Never-
theless, further research is required, and this would allow
improvements in the development of new Ni-free Ti alloys
for biomedical applications.
Considering that there are only a few studies dealing with
multicomponent TiMo alloys and their potential use as
biomaterials, the goal of this work was to design novel
biomedical Ti alloy compositions in the Ti8MoNbZr sys-
tem with lower Young's modulus and improved corrosion
resistance.
2. Materials and methods
2.1. Alloy design and fabrication processes
A series of multicomponent Ti8MoNbZr ( 2, 3, 4, 5 and
6 at%) alloys were prepared from commercially high purity Ti,
Mo, Nb and Zr metals ( 99.89% purity for all the metals) by arc
melting with a tungsten electrode on a water-cooled copper
sphere. The ingot was melted at least ve times to improve
chemical homogeneity. The obtained ingots (30 g) solution
was treated at 1000 1C under high vacuum for 24 h inside a
tabular furnace, followed by a quenching in water at room
temperature to suppress dendrite formation. It was then
swaged at 780860 1C with an 80% reduction in area. The
sample (cylindrical in shape) was solution-treated at 950 1C
under high vacuum for 2 h in a tabular furnace, and
quenched at room temperature to remove micro-segregation.
In agreement with earlier works [38,39], the composition
pleted at the Sorby Centre for Electron Microscopy and
Microanalysis, the University of Shefeld, United Kingdom
using 'Rigaku NEX QC' Energy Dispersive X-ray Fluorescence
70 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77

Table 1 The chemical compositions of the Ti8MoNbZr alloys studied by EDXRF at a resolution near 150 eV FWHM (all in
atomic%).

Materials Mo Nb Zr C Cu Si O H Ti K e/a

Ti8Mo6Nb4Zr 7.98 5.93 3.96 0.018 0.005 0.011 0.045 0.0036 Bal. 1.16 4.22
Ti8Mo5Nb3Zr 7.98 4.94 2.97 0.010 0.003 0.011 0.045 0.0036 Bal. 1.14 4.21
Ti8Mo4Nb2Zr 7.98 3.89 2.01 0.020 0.002 0.012 0.044 0.0036 Bal. 1.12 4.21
Ti8Mo4Nb5Zr 7.98 2.96 5.02 0.001 0.003 0.010 0.045 0.0036 Bal. 1.13 4.21

(EDXRF) elemental analyser. (The results are presented in
Table 1). During the study, all the elements in the sample
were excited simultaneously in the EDXRF spectrometers. An
energy dispersive detector of 150 eV, in combination with a
multi-channel analyser, was used to simultaneously collect
the uorescence radiation emitted from the sample and to
separate the different energies of the characteristic radiation
from each of the different sample elements. The increased
intensity delivered to the sample in a small focal spot allows
for enhanced spatial resolution for small feature analysis and
enhanced performance in measurement of trace elements.
For every sample, the counting interval, collimator size and
test area location were varied, and measurements were taken
ve times to reduce measurement errors. (In this work, all the
compositions are given in at% units unless otherwise noted.)
Mo, Nb and Zr are known as the best stabilising
elements. In line with Antipov and Moiseev [40], the coef-
cient of stabilisation, the stability of , is dened in Eq. (1)
as:
X ci
K i
1 initial cross section area,A0 , where, e is the engineering strain
ci
where, ci is the concentration of the stabilising element in
the alloy and ci is its critical concentration. The Ti alloys
whose K (i.e., stabilising index) is in the region of 11.5 (i.e.
1oK o1.5) was dened as metastable alloy. For Ti8Mo
alloy, the K is 1.12, which puts the alloy in the metastable
category. The K is useful both for materials science students
studying titanium and for specialists in the eld. The K
coefcient is known to be very convenient for work with
publications on newly created alloys. Previous experimental
investigations have shown that 00 and phases coexist
within 510 at% Mo threshold [4]. In effect: we chose Ti-
8 at% Mo alloy to evaluate the inuence of biocompatible
elements such as Mo, Nb and Zr on Ti phase stability, Young's
modulus and corrosion behaviour.
2.2. Microstructure observation, XRD analysis and tensile
test
Phase characterisation was carried out using X-Ray diffrac-
tion (XRD, Siemens D500 diffractometer) at room temperature
under the conditions of Cu K radiation, ( 1.5418 ) oper-
ated at 40 Kv and 30 mA. The normal coupled (2) scans
were performed at a 2 range of 20901 with a 0.02 step size
and 1 s dwell time. The phases were identied by comparison
with simulated diffractograms using the software PowderCell
version 2.4 designed by Kraus and Nolze [41], inserting data of
, 00 , and Ti phases as space groups, lattice parameters
and atomic positions. The microstructural characterisation
was investigated by scanning electron microscopy (SEM) after
using standard metallographic techniques, and then etched
in Krol's reagents (3 ml HF, 6 ml HNO3 and 100 ml H2O). The
tensile tests were carried out on an Olsen 8500 series testing
machine at room temperature, with a strain rate of 4  10  3
s  1. The dimension of test samples were 12 mmx8 mm, for
length and diameter respectively (according to ASTM D882-
11). From this equipment, the true stressstrain curve was
obtained by the following process: an extensometer was used
to record an increment of true strain, de, (the incremental
change in length, dL, divided by the length, L, at the time, de;
dL/L) and integrated to obtain true strain. The load Cell
provides an electrical circuit for measuring the instantaneous
load along the loading axis, expressed as force per unit area
of cross section, dened as
F
s 2
A0
The instantaneous cross section area,A1 , is related to the
and is the logarithmic or true strain.
A1 A0 exp  3
A0
A1 4
1 e
This expression was divided into the applied force to
obtain the values of the true stress, s, then
s sxexp s1 e 5
2.3. Ultrasound measurement of Young's modulus
The elastic modulus (EM) was determined by both tensile test
and ultrasound technique (Olympus 38DL PLUS model). The
obtained moduli values were an average of 8 measurements.
For comparison, the Young's modulus of the base alloy, Ti-
8Mo and Ti-6Al-4V were also determined under the same
condition. The elastic modulus was calculated using the
following expressions:
1 1
v 1 :  2 6
2 Ct
1 CL
E 21 vC2L 7
Here, Ct and CL are the transversal and longitudinal wave
velocities, respectively. The term is the Poisson coefcient
and the alloy density. The error is 70.25 pct, approximately,
 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77
estimated from the dimensional uncertainties and density
measurements.
2.4. Evaluation of electrochemical behaviour
The corrosion behaviour was investigated by electrochemical
testing, using the CH instrument 660D Electrochemistry
workstation in Hank's solution at 37 1C. A potentio-dynamic
polarisation scan was performed on the samples at a scan
rate of 0.333 mV s  1in the potential range of  1v to 2 v vs
SCE. Commercially pure titanium (Grade 2) was also tested for
comparison. The chemical composition of Hank's solution
includes: NaCl: 8 g/l, KCl: 0.4 g/l, CaCl2: 0.14 g/l, NaHCO3:
0.35 g/l, glucose: 1.0 g/l, MgCl2  6H2O: 0.1 g/l, MgSO4  7H2O:
0.06 g/l, KH2PO4: 0.06 g/l, and Na2HPO4  12H2O: 0.06 g/l,
equivalent to the average saline content of human body
uids [1,42]. All experiments were undertaken in a stirred
solution, maintained at 3771 1C and pH of 7.4.
3. Results and discussion
3.1. Evaluation of chemical, microstructure and X-Ray
diffraction analyses
Chemical analyses (EDXRF) were performed in many different
areas (bulk and surface), and results show that the actual
chemical composition of the alloys is close to nominal values
(Table 1), agreeing with ASTM F-67. As can be seen, all the
10 m
10 m
Fig. 1 SEM microstructure of the alloys studied in as homogenised condition (a) Ti8Mo, (b)Ti8Mo6Nb4Zr alloy, (c)Ti8Mo
4Nb2Zr alloy and (d) Ti8Mo4Nb5Zr alloy, revealing the internal structure of the specimens.
71
alloys are within  71% variance when the experimental and
nominal values were compared. The chemical composition of
the alloys was homogeneous and no expressive differences
were found between the bulk and surface of the samples,
which indicates a good homogenisation of the studied alloys.
The results obtained in this study show that the crystal
structure of the binary Ti8Mo alloys [Fig. 1(a)] is sensitive to
the Nb and Zr micro alloying concentration (Fig. 1(b)(d)).
When comparing the SEM microstructures obtained for dif-
ferent alloys, a mixture of the Bcc and orthorhombic 00
phases can be observed in large equiaxed grains of about
231779 m in diameter for the initial Ti8Mo alloy. By
contrast, the multicomponent TiMo alloys exhibit different
microstructures with smaller grain sizes. Invariably, a sig-
nicant change in property can be expected, as microstruc-
ture strongly affects almost all of the properties of materials
[45]. No signicant difference exists in the microstructures of
Ti8Mo6Nb4Zr and Ti8Mo5Nb3Zr alloys, therefore the
latter is not shown here. As seen in Fig. 1(b), a signicant
retention of the phase with smaller grains ranging from
70.3 to 10 m in diameter is observed for the Ti8Mo6Nb
4Zr alloy. The dark patches seen on the micrograph may
represent the niobium-rich phase, though it is possible that
these are merely artefacts produced during electro-polishing.
Samples prepared from a relatively hydrouoric-sulphuric
lactic acid electrolyte also exhibited a similar structure.
However, the results of the microstructural characterisation
are identical to those of Gordinet al. [43] and conrm the
expected effect of Ti replacement by Nb. This is in contrast to
10 m
10 m
72 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77
a mixture of the Bcc and orthorhombic 00 phases observed,
when the concentration of Nb added to the Ti8Mo was
reduced to 4% (See Fig. 1(c) for Ti8Mo4Nb2Zr alloy).
phase retention in Ti alloys with higher Mo concentra-
tions is in accordance with the results shown in Davis et al.
[44], which reports that in TiMo systems, the martensitic
structure changes from hexagonal to orthorhombic 00 at Mo
rates of approximately 6%. More recently, Bania [45] shows
that a minimum of 10% Mo was required to completely
stabilise the phase at room temperature. It is therefore
evident that alloy content inuences the phase constitution
of the solution-treated Ti8MoNbZr alloys.
Conversely, a signicant change in microstructure is
recorded in Fig. 1(d), due to the higher Zr content. The Ti
8Mo4Nb5Zr alloy microstructure has obvious brous
stripes. In addition, the SEM micrograph demonstrates amor-
phousness, with higher Zr content. Nonetheless, further
investigation is required, as Zr is an element of choice to
stimulating amorphous properties in metallic glass alloys
[46,47]. The stability of the alloy might be related to the
addition of Zr and the rise in exothermic energy (i.e., negative
formation energy), with the Ti ratio in the alloy caused by the
addition of neutral elements, viz: Zr (i.e. completely soluble in
both and phase in the TiZr binary diagram [29]). The study, the e/a ratio for the Ti8MoxNbxZr alloys was
stabilising effect of Zr could therefore be associated with
phase stability of the alloy, arising from the alloying elements
(Mo and/or Nb).
Fig. 2 shows the XRD proles of the multicomponent Ti
8MoxNbXZr alloys. The presence of the phase is con-
rmed in all the alloys, thus conrming the sensitivity of the
initial binary Ti8Mo alloy to the micro-additions (Nb and Zr).
Strong peaks associated with the (002), (200), (220) and (211)
diffraction planes are evident in all the samples. When
comparing the results of the different alloy samples, the
diffraction peak of orthorhombic 00 can be detected in the
Ti8Mo4Nb2Zr alloy (i.e. the alloy consisting of the least Nb
content), as indicated by the splitting of the single 0 (1010)
peak into three 00 peaks [50]. These 00 peaks are of a much
weaker intensity, or unnoticed, in the other alloys. This is
Fig. 2 XRD patterns of the alloys studied revealing the phases present.
consistent with previous microstructure observation [2022].
According to various references [2022], the amount of 00
martensite phase in Ti alloys is conditioned by the -
stabiliser content and by grain size. When Nb is low, there
exists an orthorhombic 00 phase, but when Nb is high, the 00
phase peaks become weaker and more diffuse. In line with
this nding, 00 (020), 00 (111) and 00 (021), 00 (022), 00 (131) and
00 (221) peaks exist in the Ti8Mo4Nb2Zr sample. A weaker
and more diffused 00 (020) peak appeared in the Ti8Mo4Nb
5Zr alloy, while just a single phase exists in the Ti8Mo
6Nb4Zr and Ti8Mo5Nb3Zr alloys (high Nb samples).
Clearly, with the Nb content increasing, the phase becomes
stable. The appearance of the 00 martensite in Ti8Mo4Nb
2Zr is consistent with the previous conclusion that the
martensitic transformation is grain size-dependent [9,14],
and that grain renement suppresses the martensitic
transformation.
The formation of the athermal phase in titanium alloys,
it has been reported, can be predicted by the e/a ratio [48,49].
According to various references [48,49], the formation of the
athermal phase reaches its maximum at the e/a ratio of
4.13, and its minimum at 4.30. When the e/a ratio is larger
than 4.30, the phase becomes the dominant phase. In this
calculated to be between 4.2 and 4.22 (Table 1), which is in
the range of 4.134.30. Absence of the phase in the alloys
can therefore be attributed to the high stability index of the
Nb alloy additions. This is not unexpected, as Nb is the
nearest neighbour element to the right of Mo in the periodic
table, with the closest atomic size difference.
3.2. Evaluation of lattice parameter and structural
stability
An important observation made by this study concerns the
systematic variation in the lattice constant and microchem-
istry of retained , as noted in Table 2. The decrease in lattice
constant, with increasing Nb content, is in contrast to the
expected increase in the equilibrium and increase in Nb
 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77 73

Table 2 Experimentally observed parameters of the equilibrium lattice constant of crystal structure as a func-
constituent phases and volume fraction of the phases tion of Nb content is shown in Fig. 3(a). The lattice parameter
based on XRD measurement with Cu. K1 radiation. decreases with Nb concentration. The present result suggests
Alloy/ -phase 0 0 -phase c(nm) vol% vol%, that the x dependence of the lattice constant can be tted as
Elements (nm) (nm) (7.03) (7.03) (7.03) a 4.35600.2114 ().
(7.03) (7.03) It is important to note that this linearity is in agreement
with stability and decreasing Nb content, and that this
Ti8Mo 0.318 0.304 0.464 95.1 4.9
6Nb4Zr
corresponds with the ndings of Hao et al. [35,51]. According
Ti8Mo 0.320 0.310 0.464 91.3 8.7 to these references [35,51], the result can be attributed to two
5Nb3Zr factors. The rst is that the atomic radius of the Mo
Ti8Mo 0.325 0.311 0.464 68.1 31.9 (0.136 nm) and Nb (0.146 nm) alloy additions were smaller
4Nb2Zr
than those of Ti (0.147 nm) and Zr (0.16 nm), and an alloying
Ti8Mo 0.328 0.309 0.464 89.9 10.1
element is in very small quantity in Ti8Mo6Nb4Zr, Ti
4Nb5Zr
8Mo5Nb3Zr and Ti8Mo4Nb2Zr alloys, compared to a Ti
8Mo4Nb5Zr alloy. The replacement of Ti by Mo or Nb
therefore induces shrinkage of the crystal lattice. There is a
similar effect on Ms, with the temperature reported in Ti
30TaZr [51], Ti15MoFe [52], TiCrZr [53], TiNbTa [53] and
0.330 0.330 TiNbZr [54]. The second factor is a change in the nearest
Figure 2 : XRD patterns of the alloys studied. neighbour co-ordination from approximately eight in 00 to
0.328 0.328
eightfold co-ordination in the original bcc cell, which means
a() vs Nb content
0.326 0.326 the distortion is a reection of the tendency for Mo and Nb to
break Ti bonds and retain the eightfold co-ordination
0.324 0.324
obtained in the bcc form, resulting in a reduction in the
a()
a()

0.322 0.322 lattice constant.

In order to investigate alloying behaviour and identify
0.320 0.320
metallurgical trends with regards to structural stability and
0.318 0.318 desired materials properties, we used a wide angle diffraction
to determine the volume fractions of 00 and phases for the
0.316 0.316
different alloy compositions. As noted by Pham et al. [55],
Zr

Zr

Zr

Zr
5

4
b-

b-

b-

b-

knowing the microstructure of biomedical materials, such Ti

4N

4N

5N

6N
o-

o-

o-

o-
M

M
-8

-8

-8

-8

and its alloys, is very important because the coexistence of

Ti

Ti

Ti

Ti

Nb content orthorhombic 00 Ti and bcc Ti is an important factor in

controlling mechanical properties such as yield strength,
100 100
toughness, Young's modulus and corrosion resistance, hav-
ing a direct effect on their biocompatibility.

80 80 Fig. 3(b) shows the volume fraction of the and 00 phases
as a function of the Nb content. Although and the presence of
60 60
Vol.(%)

Vol.(%)

40 40

20 20

0 0
r

r
4Z

3Z

2Z

5Z
b-

b-

b-

b-
6N

5N

4N

4N
o-

o-

o-

o-
M

M
-8

-8

-8

-8
Ti

Ti

Ti

Ti

Nb content

Fig. 3 (a) the equilibrium lattice constant of phase of

studied the Ti8MoNbZr alloys as a function of Nb content
(x), (b) volume fraction of and 00 phases for the alloys.

content. The lattice parameters of orthorhombic 00 phase

were a 0.3012, b 0.4983 and c 0.4658 nm, whilst that of
body centred phase was a 0.331 nm. The value of the
lattice parameters for and 00 phase (Table 2) were calculated Fig. 4 True stressstrain curves of the phases of studied the
using the Jean Laugier software, Celref [50]. A plot of the Ti8MoNbZr alloys at room temperature.
74 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77
orthorhombic 00 phase in metastable TiMo based alloys
has long been reported. Davis et al. [44] report that in TiMo
systems, the martensitic structure changes from hexagonal,
to orthorhombic 00 at Mo rates of approximately 6%. Accord-
ing to Fig. 4, the volume fraction of 00 phase formed in the
microstructure decreased to 10% with the addition of 4% of
Nb. The higher stability of -phase in alloys containing up to
5% Nb threshold makes it more difcult for 00 martensite
plates to nucleate. It is therefore apparent that Nb, Zr micro-
additions in this alloy system suppress the presence of
metastable phase(s), including , and 00 phases. It is noted
that the volume fraction of the retained phase increases
with Nb in the alloys. The result implies that the Ti8Mo alloy
system is sensitive to the Nb elemental additions. As shown
in Fig. 3(b) and summarised in Table 2, Nb rates of approxi-
mately 6% almost entirely suppress the 00 martensite
fraction.
3.3. Evaluation of mechanical properties
The true stressstrain curves recorded during tensile testing
of the alloys at room temperature are shown in Fig. 4 (for
details of the process, see Section 2.2). Due to the importance
of mechanical compatibility, the elastic modulus was care-
fully measured using strain gauge and ultrasonic wave
measurements (See Table 3). The results show that all the
alloys, except Ti8Mo4Nb2Zr (i.e. Ti8Mo6Nb4Zr, Ti8Mo The electrochemical behaviours of the various Ti8MoNb
5Nb3Zr, Ti8Mo4Nb2Zr and Ti8Mo4Nb5Zr) exhibited a Zr-based alloys studied, and the CpTi during immersion in
single stage yielding behaviour. The true stressstrain prole
exhibited by samples Ti8Mo6Nb4Zr, Ti8Mo5Nb3Zr and observed that the polarisation curves of the alloys are similar.
Ti8Mo4Nb5Zr show considerably higher strengths of
899 MPa, 947 MPa and 798 MPa, respectively, with a gentle
slope in the elastic region, and outstanding work hardening
after the yielding. Conversely, the alloy Ti8Mo4Nb2Z
reveals a 'plateau' at 485 MPa in the stressstrain curve,
characterising the super-elastic behaviour of martensitic
alloy. This can be physically interpreted as the result of the
stress relaxation accompanying the nucleation and growth of
martensite (00 ) in the austenitic matrix (). This behaviour is
ascribed to the associated shear of local regions being
generated by the thermo-elastic martensitic 00 phase in
metastable -Ti alloys. Although the alloy exhibits a low
strength, the elastic modulus of 35.4 GPa is signicantly
lower, comparable to human bone, and the ductility is much
higher than other alloys already being used in biomaterials
implant applications.
A literature review was done to compile a complete list of
low elastic modulus or shape memory alloys (See Table 3).
Table 3 shows the mechanical properties and the ratio of
strength to modulus of the alloys compared to typical
biomaterials [1216].
As mentioned in the previous section, an ultrasound
technique was employed to determine the elastic modulus.
In comparison to the strain gauge measurement, the ultra-
sound tests of the bulk samples showed small elastic moduli
values of 72 GPa, 69 GPa, 35 GPa and 52 GPa for Ti8Mo6Nb
4Zr, Ti8Mo5Nb3Zr, Ti8Mo4Nb2Zr and Ti8Mo4Nb5Zr to that of biomedical Cp Ti (grade 2) metal. Thus, the values
alloy samples, respectively, with an estimated error of 73%,
while the former indicated 75 GPa, 72 GPa, 37.5 GPa and
60 GPa, respectively.
A literature review was done to compile a complete list of
low elastic modulus or shape memory alloys (Table 3). The
elastic moduli of the studied alloys were relatively low,
compared with alloys currently employed in the biomedical
eld. A more reduced modulus of the Ti8Mo4Nb2Zr alloy,
as observed by the authors, can be ascribed to the presence of
the 00 plates, which presents a modulus about half that of the
phase [25]. The latter is attributed to a remarkable capacity
of the 00 plates for absorbing the transmitted waves, which
creates a distortion of the wave velocity, and, consequently,
the elastic modulus measured is also affected [26]. The
Young's modulus of Ti8Mo4Nb2Zr (Table 3), which is
much closer and comparable to natural bone, can minimise
the bone resorption that arises from the stress shielding
effect and consequently increase the long-term stability of
the implants. Thus, these alloys are expected to be a promis-
ing candidate for biomaterials. Appropriate alloy optimisa-
tion and solution treatment can therefore be an effective way
of suppressing the formation of athermal phase in the Ti
Mo alloy systems to exhibit a much lower elastic modulus
and a much needed higher ratio of strength modulus value.
Additionally, the alloying elements in this alloy have been
developed as commercial biomaterials grades [34].
3.4. Electrochemical characterisation: corrosion resistance
Hank's solution at 37 1C, are presented in Fig. 5. It can be
Although all the alloys exhibited spontaneous passivation
behaviour in the test environment, there is no evidence of
activepassive transition. This indicates that the oxide lm
spontaneously developed at the surface of the alloys upon
immersion in the test electrolyte exhibited passivation char-
acteristics, which is a feature previously observed in some Ti-
based alloys, such as TiNi [57,58] and TiNbHf [59]. The
mean value and standard deviations of corrosion parameters
obtained by Tafel plot, using both anodic and cathodic
branches of the polarisation curves, are listed in Table 4.
The present result is consistent with previous observa-
tions by Glass [18] and Hong [19], which suggest that the
addition of Mo increases the thermodynamic stability of
titanium, due to low diffusivity, which invariably promotes
the resistance to pitting corrosion. Similarly, the results
obtained here reveal an improvement in corrosion protection
characteristics, which may be attributed to the low diffusivity
of niobium in the alloys. Consequently, nobler values for Ecorr
(namely  0.301rEcorr r  0.326) accompanied by smaller
current densities jcorr (namely 0.214r jcorr r 0.24) and passive
current density jpass (namely 1.9r jpass r 1.98) were obtained
in this work. This is similar to the experimental results
obtained by Lee et al. [60] in its comparison of the corrosion
behaviour of a series of cast TiNb in Hank's solution.
The electrochemical results presented in Table 4 reveal
that the corrosion resistance of the samples are comparable
given in Table 4 can be used to provide a relative biomedical
ranking of the corrosion resistance of the alloys. The pitting
corrosion was simulated by polarising the specimen to noble
 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77 75

Table 3 Mechanical properties of typical biomaterials and shape memory alloys and the four Ti8MoxNbxZr alloys
studied compared.

S/N Reported alloy E (GPa) YS (MPa) Ratio of strength to modulus [  10  3] [%] Ref.

1 Ti8Mo6Nb4Zr 72 899 12.3 15 This work

2 Ti8Mo5Nb3Zr 69 947 13.9 21 This work
3 Ti8Mo4Nb2Zr 35.4 798 12.3 15 This work
4 Ti8Mo4Nb5Zr 52 483 10.7 26 This work
5 Ti6Al4V 113 1100 1.74.7 1316 [61]
6 Ti5Al2.5Fe 110 1020 [5]
7 Ti6Al7Nb (swaged) 105 900 12 [62]
8 CP Ti(Grade 14) 102.7 170485 1.74.7 1524 [7]
9 Ti6Al7Nb(soln.) 110 1101050 21 [62]
10 Ti13Nb13Zr 7984 9731037 [28]
11 Ti12Mo6Zr2Fe 7485 10601100 [29]
12 Ti15M0(aged) 78 448 7 21 [10,61]
13 Ti35Nb7Zr5Ta 55 823 [10]
14 Ti29Nb13Ta4.6Zr 63 400 [10]
15 Ti24Nb4Zr7.9Sn 46 700 16 [10]
16 Ti29Nb13Ta2Sn 48 469 [10]
17 Ti29Nb13Ta6Sn 65 523 [10]
18 Ti29Nb13Ta4.6Sn 78 513 [10]
19 TIMETA 83 [5,10]
20 Tiadyne 1610 81 [5]
21 Gum Metal 40 [31]
22 Ti15Mo2.8Nb3Al 82 [10]
23 Ti35Nb5Ta7Zr0.4O 66 1010 19 [39,2,21]
24 Ti16Nb13Ta4Mo 98 21.3 [22]
25 Ti15Zr4Nb4Ta0.2Pd 97 [19]
26 Ti30Nb10Ta5Zr 66.9 804 [19]
27 Ti15Mo3Nb0.3O 82 [10]
28 Ti15Mo5Zr3Al 75 8381060 [10]
29 Ti29Nb13Ta 103 [10]
30 Ti34Nb9Zr8Ta 89 [28]
31 Ti13Mo7Zr3F 89 [28]
32 Ti14Nb 98 [63,64]
33 Ti18Nb 85 [63,64]
34 Ti22Nb 80 [63,64]
35 Ti26Nb 78 [63,64]
36 Ti30Nb 80 [63,64]
37 Ti32Nb 85 [63,64]
38 Ti34Nb 90 [63,64]
39 Ti36Nb 70 [63,64]
40 Ti38Nb 65 [63,64]
41 Ti40Nb 55 [63,64]
42 Ti17.4Nb8.1Ta3.4Zr 55.3 [51,63]
43 Ti16.1Nb8.2Ta3.4Zr 64.9 [51]
44 Ti20.5Nb4.5Ta5.1Zr 50 [51]
45 Ti24.1Nb1.7Ta5Zr 55.7 [51]
46 Ti24.2Nb2Ta5.1Zr 48 [51]
47 Ti7.5Mo 55 [36,61,63]
48 Ti10Mo 95 [31,63]
49 Ti40Nb1Hf 65 [64]
50 Ti40Nb3Hf 62 [64]
51 Ti40Nb5Hf 67 [64]
52 Ti40Nb7Hf 63 [64]
53 Ti13Nb13Zr 7984 [62]
54 Ti15Mo (ann.) 78 448 7 21 [61,63]
55 Ti15Mo5Zr3Al 80 532 5 12.6 [61]
56 Ti12Mo3Nb(soln.) 105 450 4.3 41.2 [61]
57 Ti50Ta 88 380 4.3 25 [61]
58 ASTMF75(CoCrMo) 220 825869 7.27.9 610 [61]
59 Ti2448 (Ti24Nb4Zr8Sn) 42 476 6.5 7.3 [5,63]
60 Cortical Bone 28.840 [5,35]
76 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77

potentials, until the oxide layer broke down. The passive
layer, mainly consisting of TiO2 and Nb2O5, preferentially
forms and protects against biochemical reactions and corro-
sion [22]. The passive current densities were much lower for
alloys with higher niobium content due to the formation of a
very stable niobium oxide layer (NbO5) on the metal surface
[56]. The improved corrosion and modulus properties mean
that the alloys could be introduced as alternative to the
materials currently used in orthopaedic implant application.
4. Conclusions
This study considers the effect of the micro-alloying of
niobium and zirconium additions to TiMoxNbxZr (x 26)
alloy, keeping the molybdenum content close to 8 at% to
investigate the microstructural evolution, mechanical and
corrosion resistance of the materials in Hank's solution at
37 1C. In order to prevent stress shielding and avoid bone
resorption, tensile testing and ultrasonic measurements were
carried out and the following conclusions were drawn.
(1) The microstructure and phase stability of the alloys are
dependent upon alloying additions. The results indicate
2
(Cp-Ti)
1
(Ti-8Mo-5Nb-3Zr)
(Ti-8Mo-6Nb-4Zr)
Potential (V)
that a signicant microstructural sensitivity was appar-
ent, with Nb and Zr micro-additions to this Ti8Mo alloy
system. This invariably has led to the dramatic change in
some properties, including a lower Young's modulus,
better toughness and high elongation to failure exhibited
by Ti8Mo4Nb2Zr alloy.
(2) Combining Nb and Zr alloying elements in appropriate
synergy impedes formation of the athermal phase,
which causes embrittlement that has been a main con-
cern for their mechanical applications. Thus, a signicant
amount of phase was retained in the alloy as a result of
the micro-addition.
(3) The result based on combined use of tensile test and
ultrasonic measurements shows that Nb and Zr micro-
additions to this Ti8Mo alloy system improved the elastic
modulus of all the alloys. The low elastic modulus of
35.4 GPa and high elongation to failure exhibited by Ti
8Mo4Nb2Zr alloy indicate it is more suitable for biome-
dical applications than most conventional metallic bio-
materials from a better mechanical compatibility
perspective. It could potentially be used to prevent stress
shielding and bone resorption in orthopaedic implant
applications.
(4) The improvement in corrosion resistance of the alloys in
Hank's solution achieved through the addition of non-
toxic elements (Nb and Zr) to Ti8Mo alloy system is
notable. Potentio-dynamic polarisation data show that
both corrosion and passive current densities decrease
when Nb content increases. The signicant corrosion
resistance and non-toxicity are therefore properties perti-
nent to long-term stability of orthopaedic implants,

(Ti-8Mo-4Nb-2Zr) because materials used as implants are expected to be

(Ti-8Mo-4Nb-5Zr)
0 highly non-toxic and should not cause any inammatory
or allergic reactions in the human body. The results show
that the alloys could potentially be used for biomedical
proposes.
-1

Acknowledgement
1E-8 1E-7 1E-6 1E-5 1E-4
Current (A)
The funding through the Centre for Adaptive Manufacturing/
Fig. 5 Potentiodynamic polarisation curves for the Ti8Mo Mercury Centre initiative of the Department of Materials
xNbxZr(x 25) and CpTi after 2 h immersion in Hank's Science and Engineering, University of Shefeld, United King-
solution at 37 1C, scanning rate: 0.5 mV/s. dom is gratefully acknowledged.

Table 4 Corrosion parameters (and standard deviation values) determined from the potentio-dynamic polarisation curve
measured for the Ti-8Mo-xNb-xZr(x 2-5) in Hank's solution at 37 1C.

Alloy The corrosion parameters (and standard deviation values) determined for the Ti8MoNbZr alloys

Ecorr (VSCE) jcorr ( cm  2) jpass ( cm  2) Reference

CPTi 0.33 (0.021) 0.33 (0.07) 2.17 (0.04) This work

Ti6Al4V 0.327 ( ) 0.326 ( ) 0.323 (  ) [61]
Ti8Mo6Nb4Zr 0.301 (0.021) 0.214 (0.07) 1.9 (0.05) This work
Ti8Mo5Nb3Zr 0.316 (0.022) 0.217 (0.06) 1.92 (0.04) This work
Ti8Mo4Nb2Zr 0.32 (0.020) 0.22 (0.05) 1.97 (0.05) This work
Ti8Mo4Nb5Zr 0.326 (0.019) 0.24 (0.05) 1.98 (0.04) This work
 journal of the mechanical behavior of biomedical materials 60 (2016) 68 77 77

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