M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9

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Fatigue behaviour of boron free and boron containing heat

treated Ti-13Zr-13Nb alloy for biomedical applications

P. Majumdar⁎, S.B. Singh, M. Chakraborty

Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur, India

AR TIC LE D ATA ABSTR ACT

Article history:
Received 7 December 2009
Received in revised form
2 September 2010
Accepted 4 October 2010
Fatigue behaviour of heat treated Ti-13Zr-13Nb (TZN) and Ti-13Zr-13Nb-0.5B (TZNB) alloys
for biomedical implants has been investigated by rotating bending test. It was found that
fatigue strength of TZN and TZNB alloys is comparable with that of conventionally used
biomedical titanium alloys. Addition of boron to TZN alloy deteriorates fatigue strength.
© 2010 Elsevier Inc. All rights reserved.

Keywords:
Titanium alloy
Microstructure
Fatigue
SEM

1. Introduction fatigue strength by increasing the crack initiation resistance.

Titanium and its alloys have become one of the most
attractive classes of biomedical implant materials. They are
generally preferred to stainless steels and Co–Cr alloys
because of their low density, superior biocompatibility and
corrosion resistance, good mechanical properties and low
elastic modulus [1–6].
Fatigue is one of the most important properties of biomater-
ials especially when biomaterials are used under condition of
cyclic loading [7,8]. A hip prosthesis may be subjected to
dynamic loading of about 1 to 2 million load cycles per year
with articulating forces reaching 3 to 5 times the body weight [4].
Simple walking results in a hip prosthesis being subjected to a
cyclic loading at about 1 Hz [9]. The fatigue life of a metallic
implant is sensitive to prior thermomechanical treatment. For
example, aging treatment of β solution treated and rapidly
cooled β titanium alloys improves the fatigue strength by
transforming the β phase into two phase α + β microstructure
[10]. Homogeneous precipitation of fine α phase increases the
However, aging increases the elastic modulus of the alloy and
thereby eliminating the advantage of modulus reduction
associated with β alloys [10,11]. Long et al. [10] have suggested
that the fatigue properties of the titanium alloys may be
improved by altering the interstitial content (O, C, N, H etc.).
However, the role of the interstitial element boron on the fatigue
life of the titanium alloys has not been studied yet.
The work presented here primarily aims at synthesis of
boron free and boron containing ‘near-β’ titanium alloys and
proper design of the processing and heat treatment schedule
of the alloys in order to produce an appropriate microstructure
to provide suitable mechanical properties for implants. The
focus of the present work is on fatigue properties only. Other
mechanical properties are discussed elsewhere [12].
The fatigue test of metallic implants for biomedical
applications is often performed in simulated body fluid (SBF)
in order to create clinically relevant atmosphere so that the
effect of corrosion on fatigue behaviour can be assessed.
However, it has been found that the simulated body fluid (SBF)

⁎ Corresponding author. Department of Metallurgical and Materials Engineering, Indian Institute of Technology, Kharagpur Kharagpur-721302,
India. Tel.: +91 3222 283290; fax: +91 3222 282280.
E-mail addresses: m.pallab@gmail.com, pallab@metal.iitkgp.ernet.in (P. Majumdar).

1044-5803/$ – see front matter © 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2010.10.004
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9
has no noticeable effect on the fatigue limit; it is the
mechanical and metallurgical parameters that have the
main effect on the fatigue strength [8,11,13]. Boehlert et al.
[8] have observed that the fatigue behaviour of Ti-21Al-29Nb
and Ti-15Al-33Nb alloys was not significantly affected when
tested in Ringer's solution. This lubricant was found to neither
degrade nor improve the fatigue strength and no significant
differences were observed between the fracture surfaces of the
samples tested in Ringer's solution and air [8]. Therefore, the
fatigue limit of the alloy in simulated body fluid is expected to
be similar to that in air. Hence, in the present investigation the
fatigue strength of the material was evaluated in air only.
2. Experimental Procedure
Ti-13Zr-13Nb (TZN) and Ti-13Zr-13Nb-0.5B (TZNB) alloys
(compositions in wt.%) were prepared in the form of a
cylindrical ingots by arc melting with a non consumable
tungsten electrode under high purity argon atmosphere in a
vacuum arc melting unit supplied by Vacuum Techniques Pvt
Ltd, Bangalore. The ingot was given 30–40% reduction by rolling
at two different temperatures (800 °C i.e. above β transus and
650 °C i.e. below β transus) and then air cooled to room
temperature. The samples were solution treated at their
respective hot rolling temperature (800 °C or 650 °C) for 1 h in
dynamic argon atmosphere and then water quenched (WQ).
Water quenched samples were aged at 500 °C for 5 h. Detailed
studies reported elsewhere have shown that this heat
treatment schedule gives the optimum combination of
mechanical properties (modulus, YS, UTS, elongation etc.)
for biomedical application and therefore, this heat treatment
schedule was selected for fatigue studies.
Optical microscopy was used for microstructural exami-
nation of the heat treated samples. The polished samples
were etched with Kroll's reagent (10 vol.% HF and 5 vol.% HNO3
in water). For more detail studies of the TiB precipitates, TZNB
alloy was examined on scanning electron microscope, FEI
Quanta ESEM operated at 20 kV using the backscattered
electron (BSE) imaging modes.
Fatigue tests were conducted using Wohler rotating fatigue
machine, HSM19 MK III, supplied by Hi-Tech education, UK.
Schematic drawing of fatigue specimen is given in Fig. 1. This
machine applies the method of reversing the stress on a part by
employing a cantilever rotated at 1435 rpm about its longitudinal
axis. Hence the stress at any point on the surface of the cantilever
varies sinusoidally. The cantilever is specially designed to use a
simple specimen with a definite minimum cross section. The
fatigue experiments were carried out under the condition of
completely reversed cycles of stress (R=σmin /σmax =−1.0). Before
Fig. 1 – Geometry of the fatigue specimen (all dimensions are
in mm).
1395
fatigue testing, the machined specimens were sequentially
polished to a roughness (Ra) of 0.5–0.8 μm using 2/0, 3/0, and 4/0
emery papers. The highest stress at which the specimen did not
failed after 107 cycles is defined as a fatigue limit in this study. The
initial load was chosen at a higher level estimated at about 75% of
the YS. The stress was gradually reduced from this value until the
specimen was able to sustain 107 cycles. Three samples were
tested at each load and their average value is reported.
After fatigue testing, the fracture surfaces of tensile and
fatigue samples were examined on a scanning electron
microscope (SEM) (Model: JSM-5800, JEOL, Japan) at 20 kV
operating voltage.
3. Results and Discussion
3.1. Microstructure
Hot rolling of TZN alloy at 800 °C and water quenching from
the same temperature (800 °C) resulted in formation of
martensite with some amount of retained β phase (Fig. 2).
Aging at 500 °C for 5 h of this water quenched sample
transformed the martensite into α and β phases and produced
fine distribution of globular α along the pre-existing martens-
ite plates (Fig. 3a). Solution treatment at 800 °C (above β
transus) led to the formation of β phase in the TZN alloy. Fast
cooling from the above temperature produced martensite in
the microstructure. It is known that martensite structure can
be produced if the cooling rate from the β phase field is
sufficiently high [14,15]. During aging of this water quenched
sample the martensite phase decomposed into α + β phase
through diffusion controlled process. For the similar heat
treatment condition, TZNB alloy showed precipitates of
titanium boride (TiB) in the matrix and some growth of the α
phase (Figs. 3b and 4).
For the sample deformed and solution treated at 650 °C
which is well below β transus, fine globular and elongated α in
the β matrix was seen in the microstructure after water
quenching. Heavy deformation (>30%) at temperatures below
the transus is expected to produce worked structure in the
material and α phase is nucleated during the plastic
Fig. 2 – Microstructure of the TZN alloy hot rolled at 800 °C
and water quenched from the same solution treatment
temperature (800 °C).
1396 M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9

The aging of this water quenched sample at 500 °C for 5 h led

to the growth of α while retaining the overall morphology of
the water quenched samples (Fig. 5a). Aging led to growth of
pre-existing α and some amount of β transformed to α during
aging. In case of TZNB alloy, after similar water quenching and
aging treatment, pronounced growth of the primary α phase
along with the formation of TiB particles was observed in the
microstructure (Fig. 5b). The detailed microstructure observa-
tions are reported in a previous study [12].
The solubility of boron in titanium is negligible [18] and
even in the temperature range of 700 °C to 1300 °C the
solubility of boron in titanium is less than 0.05 wt.% [19].
Hence it is expected that entire amount of B precipitates out as
boride particles. The TiB precipitates act as nucleation sites for
the α phase [20]. Analysis of optical micrographs indicates that
the growth of primary α is enhanced by the presence of boron
in the alloy which is more pronounced in case of solution
treatment below β transus. Banerjee et al. [18] have shown
that addition of 2 wt.% boron modifies the microstructure of
the matrix of Ti-6Al-4V alloy. The morphology of a large
number of α changes from Widmanstätten lath α to equiaxed
α. The precipitation of TiB particles also leads to the
refinement of microstructure [21,22]. In the present study
also, presence of boron was found to alter the matrix
microstructure in TZNB alloy.

Fig. 3 – Microstructures of the (a) TZN and (b) TZNB samples

aged at 500 °C for 5 h after hot rolling at and water quenching
from 800 °C.

deformation. Elongated α is formed in the water quenched

sample because of incomplete recrystallization of deformed α
due to faster cooling. Martensite was not found after water
quenching from 650 °C due to enrichment of β with Nb as a
result of partitioning of alloying elements during solution
treatment at 650 °C [16,17]. This reduces the Ms temperature of
the untransformed β to below room temperature [17] and thus
no martensite was formed on water quenching from 650 °C.

Fig. 5 – Microstructures of the (a) TZN and (b) TZNB samples

Fig. 4 – Backscatter SEM micrographs of the TZNB alloy aged at 500 °C for 5 h after hot rolling at and water quenching
showing the presence of TiB particles. from 650 °C.
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9
3.2. Fatigue Behaviour
The S–N (maximum cyclic stress vs. number of cycles to
failure) curves of the aged TZN and TZNB alloys are presented
in Fig. 6. In this study, the maximum stress at which the
specimen did not fail at 107 cycles was considered as the
fatigue limit. In case of TZN alloy, the sample that was
deformed and solution treated at 800 °C followed by water
quenching and aging showed fatigue strength of 580 MPa
(Fig. 7). On the other hand, the fatigue strength of the TZN
sample subjected to deformation and solution treatment at
650 °C followed by water quenching and aging was measured
to be 500 MPa. When similar heat treatment conditions
(solution treatment at 800 °C as well as 650 °C) were applied
on TZNB alloy the fatigue limit was found to be 540 MPa and
470 MPa respectively (Fig. 7).
Fatigue failure is by and large related to the initiation and
propagation of small fatigue cracks [7,8]. The cracks can be
generated at slip bands in α phase, at the interface between
α–β phases or there can be slipless cracking of α phase [23].
Aging at 500 °C for 5 h after water quenching from a solution
treatment temperature of 800 °C transforms the martensite
into α and β phases and produces fine globular α on the pre-
existing martensite plates resulting in higher fatigue strength.
Fig. 6 – S–N curves of the aged (a) TZN and (b) TZNB alloys;
samples were deformed and solution treated at 800 °C or
650 °C followed by water quenching and aging.
1397
Fig. 7 – Fatigue strength at 107 cycles of the aged TZN and
TZNB alloys; samples were deformed and solution treated at
800 °C or 650 °C followed by water quenching and aging.
On the other hand, the sample solution treated at 650 °C for
1 h followed by water quenching shows equiaxed primary α
and retained β. The aging of this water quenched sample leads
to β to α transformation and growth of primary α and this
leads to inferior fatigue strength of the sample. Coarsening of
α phase can lead to a decrease in the resistance to crack
initiation. Akahori et al. [11] have also observed that homo-
geneous precipitation of fine α phase in the microstructure
increases fatigue strength by increasing crack initiation
resistance.
Examination of the fatigue surfaces of the test samples was
done using SEM in order to determine the mechanism of the
fatigue failure (Figs. 8 and 9). Three distinct zones viz. crack
initiation zone, crack propagation zone and over-load zone
were observed in the SEM photographs. It was observed that
the fatigue cracks mainly initiated from the surface of the TZN
alloy (Fig. 8a) and from subsurface area of the TZNB alloy
(Fig. 9a). Once initiated, the fatigue cracks started to propagate
towards the specimen interior. The fracture surface in the
crack initiation and stable crack growth regions were relative-
ly flat for TZN alloy (Fig. 8b) whereas it was more tortuous for
TZNB surface (Fig. 9b). The fracture surface of the final stage
over-loading zone consisted of small dimples which are more
evident in TZN alloy (Fig. 8c) than in TZNB alloy (Fig. 9c).
The results obtained from the fatigue experiment of this
study revealed that the fatigue strength of TZNB alloy was
lower than TZN alloy. Soboyejo et al. [24] found that a small
amount (~2.5 vol.%) of TiB whiskers may degrade the overall
fatigue life of Ti-6Al-4V. This is because of the premature
nucleation of fatigue cracks due to cracking of TiB whiskers,
and the interfacial decohesion that occurs around the TiB
whiskers within the first 20% of life. Furthermore, it has been
shown that near-threshold fatigue crack growth rate in the
composite is faster than that in the matrix material processed
under the same nominal processing conditions [24]. Chen et
al. [25] also found that for the cast-and-extruded alloys, Ti-
6Al-4V exhibited longer average fatigue lives than B-modified
Ti-6Al-4V. This is believed to be a result of the strong α-phase
texture in the cast-and-extruded Ti-6Al-4V alloy as compared
with the B-containing cast-and-extruded alloys [25].
On the other hand, Chen et al. [26] observed that a small B
contents of less than 1 wt.% were beneficial to the fatigue life
1398 M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9
Fig. 8 – SEM images of fatigue fracture surface of TZN alloy;
sample deformed and solution treated at 650 °C followed by
water quenching and aging at 500 °C (a) crack initiation area;
(b) crack propagation area and (c) fractured area.
of boron-modified Ti-6Al-2Sn-4Zr-2Mo-0.1Si (wt.%) alloy at
high temperature because of higher elongation-to-failure ef
values. It has also been reported that compared with cast Ti-
6Al-4V alloy, boron containing cast Ti-6Al-4V material exhib-
ited longer average fatigue lives at elevated temperature. This
was attributed to the grain refinement effect of the boron,
higher εf value, load-sharing mechanism by the strong and
stiff TiB phase that precipitated as well as its presence as a
barrier to dislocation motion [25,27]. In the present work
however, all the fatigue tests were done at room temperature.
In the present investigation, boron forms TiB precipitates
in the matrix. These TiB particles act as stress concentration
Fig. 9 – SEM images of fatigue fracture surface of TZNB alloy;
sample deformed and solution treated at 650 °C followed by
water quenching and aging at 500 °C (a) crack initiation area;
(b) crack propagation area and (c) fractured area.
sites which easily nucleate crack during fatigue testing and
therefore the fatigue strength of the material decreases.
Subsurface crack initiation of TZNB alloy is considered to
occur due to slip plane decohesion, which is initiated near the
TiB particles. This is because dislocations accumulate near
very fine TiB particles, as slip cannot propagate actively in the
TiB phase. In case of TZN alloy, the inherent material property
and in case of TZNB alloy, the presence of TiB particles seems
to significantly influence the fatigue performance of the
alloys.
In the present study, the fatigue strength of the aged TZN
alloy was found to be in the range of 580 to 500 MPa and that of
 M A TE RI A L S C H A RAC TE RI ZA T ION 6 1 ( 2 01 0 ) 1 3 9 4–1 3 9 9
TZNB alloy varied from 540 to 470 MPa. It has been reported that
fatigue strength of biomedical titanium alloys (pure Ti, α + β Ti
alloys and β Ti alloys) at 107 cycles varies from 265 MPa to
816 MPa [28]. Hence, the fatigue strength of presently investi-
gated TZN and TZNB alloys is comparable with that of
conventionally used biomedical titanium alloys.
4. Conclusions
In the present work, fatigue behaviour of heat treated Ti-13Zr-
13Nb (TZN) and Ti-13Zr-13Nb-0.5B (TZNB) alloys for biomed-
ical implants has been studied; the following conclusions
drawn from the work are listed below:
1) The microstructure of the TZN alloy that was hot rolled and
solution treated at 800 °C (above β transus) followed by
water quenching and aging consisted of fine globular α
along the pre-existing martensite plates in β matrix.
2) In case of hot rolling and solution treatment of TZN sample
at 650 °C (well below β transus) elongated α and retained β
is formed in the water quenched sample. Aging led to
growth of pre-existing α and some amount of β trans-
formed to α during aging.
3) Boron leads to the formation of dispersed acicular TiB
precipitate and enhances the growth of α phase in TZN
alloy.
4) The fatigue strength of the presently investigated aged TZN
and TZNB alloys varies 580–500 MPa and 540–470 MPa,
respectively.
5) Addition of boron to TZN alloy deteriorates the fatigue
strength.
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