Journal of Alloys and Compounds 775 (2019) 158e167

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Adjustment of the microstructure and selected mechanical properties

of biomedical Ti-15Zr-Mo alloys through oxygen doping
D.R.N. Correa a, b, c, *, P.A.B. Kuroda b, c, M.L. Lourenço b, c, M.A.R. Buzalaf d, C.R. Grandini b, c
a
IFSP e Federal Institute of Education, Science and Technology of Sa~o Paulo, Grupo de Pesquisa em Materiais Meta licos Avançados, 18095-410, Sorocaba, SP,
Brazil
b
UNESP e Univ Estadual Paulista, Laborato rio de Anelasticidade e Biomateriais, 17.033-360, Bauru, SP, Brazil
c
IBTN-Br, Institute of Biomaterials, Tribocorrosion and Nanomedicine-Brazilian Branch, 17.033-360, Bauru, SP, Brazil
d
USP e Universidade de Sa ~o Paulo, Faculdade de Odontologia, Departamento de Ci^ gicas, 17.012-901, Bauru, SP, Brazil
encias Biolo

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

Article history: This study investigated the effect of oxygen doping on the crystalline structure, microstructure, and
Received 27 April 2018 selected mechanical properties (Vickers microhardness, Young's modulus and internal friction) of Ti-
Received in revised form 15Zr-xMo (x ¼ 5, 7.5, 10, 15 and 20 wt%) alloys for use as biomaterials. The monitoring of oxygen pres-
24 August 2018
sure along with the doping treatment indicated that the interstitial element was successfully absorbed
Accepted 9 October 2018
Available online 10 October 2018
into the samples. Results showed that oxygen content slightly altered the a”/b phase proportion and b
phase crystalline parameter without abruptly changing their microstructure. Moreover, the selected
mechanical properties suffered variations in a non-linear manner. Oxygen content was found to be
Keywords:
Biomaterial
suitable to produce small variations in the microstructure and in the selected properties of biomedical Ti
Ti alloy alloys, keeping the main composition unchanged.
Oxygen © 2018 Elsevier B.V. All rights reserved.
Microstructure
Hardness
Young's modulus

1. Introduction
Metallic materials are extensively employed as hard-tissue re-
placements, mainly as orthopedic and dental implants [1]. Tita-
nium (Ti) and its alloys have been attractive for use as biomaterials
because of their remarkable high strength-to-density ratio, excel-
lent corrosion resistance, relatively low Young's modulus, and
recognized biocompatibility [2]. Moreover, Ti-6Al-4V (wt%) alloy is
one of the most used biomedical implants, and the long-term
release of toxic Al and V ions has been linked to neurological
problems and adverse tissue reactions in the body [3]. Furthermore,
the mismatch of Young's modulus between the implanted material
and adjacent bone tissues has been the main cause of the stress
shielding effect [4]. Therefore, the development of new biomedical
Ti alloys targets materials with a combination of low Young's
modulus and non-toxic composition [5].
Non-toxic substitutional (e.g., zirconium, molybdenum,
* Corresponding author. IFSP e Federal Institute of Education, Science and
Technology of S~
ao Paulo, 18095-410, Sorocaba, SP, Brazil.
E-mail address: diego.correa@ifsp.edu.br (D.R.N. Correa).
tantalum, niobium, tin, and iron) and interstitial (e.g., carbon, ni-
trogen, oxygen, and hydrogen) alloying elements are currently
applied to the design of biomedical Ti alloys [6,7]. Ti-15Zr-Mo
system alloys have been recently developed for biomedical appli-
cations, with their combined non-toxic composition [8], low
Young's modulus [9], heat-treatable microstructure [10], tribo-
corrosion resistance [11], and adequate biocompatibility [12].
Specifically, Ti-15Zr-15Mo alloy exhibits superior grouping of
properties than the biomedical cp-Ti and Ti-6Al-4V alloys [12,13].
Oxygen is a hardener element that has large solubility in both
allotropic crystalline structures of Ti (bcc and hcp) [14,15]. The
element can act on the suppression of the metastable u phase and
change the b-transus temperature [16,17]. In general, oxygen tends
to improve the mechanical strength and corrosion resistance of Ti
alloy, but its relation is not fully understood [18,19]. The main ad-
vantages of oxygen in comparison with substitutional elements are
its easy availability, low effect on the density, and inexpensive cost
[20]. Therefore, the tailoring of the amount of oxygen in Ti alloys
can be an interesting route to design novel metallic biomaterials.
This study aimed to adjust the microstructure and some me-
chanical properties of Ti-15Zr-xMo (x ¼ 5, 7.5, 10, 15, and 20 wt%)
for use as biomaterial through oxygen doping treatments. The

https://doi.org/10.1016/j.jallcom.2018.10.105
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167
oxygen content was added by gas charge at distinct pressures (0,
101, 100, and 101 Torr) to incorporate the different amounts of
interstitial element in the metallic matrix.
2. Materials and methods
Ingots of Ti-15Zr-xMo (x ¼ 5, 7.5, 10, 15, and 20 wt%) alloy were
produced by argon arc-melting, using commercially pure metals.
Details about the initial chemical composition of the samples have
been described elsewhere [12]. The materials were subsequently
hot-rolled at 1273 K and air cooled, annealed in vacuum (105 Torr)
at 1273 K for 86.4 ks, and then furnace cooled. Oxygen doping
treatments were conducted by gas charge in a quartz tube. In brief,
the samples were heated in an ultra-high vacuum (106 Torr) until
1123 K, followed by oxygen gas charge, maintained for 7.2 ks, and
then water cooled. The time and temperature of doping treatments
were preliminarily set up based on the second Fick's law, for a
complete incorporation of oxygen inside the samples, as indicated
by Vicente and Grandini [21]. The quenching step was applied to
retain b phase grains with low average size, aiming an improve-
ment in the mechanical strength. Oxygen gas pressure was inserted
at 0, 101, 100, and 101 Torr. The absorbed amounts of oxygen were
measured by infrared absorption (LECO TC-400).
Crystalline structure and phase composition were analyzed by
X-ray diffraction measurements (XRD; Rigaku D/Max 2100PC) us-
ing CuKa radiation (l ¼ 0.1544 nm) at 20 mA and 40 kV. The XRD
patterns were obtained by the powder method, with step size of
0.02 , and collecting time of 3.2 s. Quantitative phase analyses were
performed by Rietveld refinement using the GSAS/EXPGUI software
with crystallographic sheets [22,23]. The instrumental parameters
for previous calibration was made by using a standard Y2O3 sample.
The quality of the refinements were monitored by the alignment of
the experimental and theoretical curves in the visual plot and by
the merit parameters (Gof, RF2, Rwp and Rp), in according to the
literature [24]. Microstructural analysis was performed by optical
microscopy (Olympus BX51M microscope) and scanning electron
microscopy (SEM; EVO LS15, Carl Zeiss microscope). The samples
were submitted to standard metallographic procedures composed
by grinding with SiC water-proof sandpapers, polishing with
alumina and diamond colloidal suspensions, and etching with
Kroll's solution (H2O, HNO3, and HF).
The selected mechanical properties were evaluated by Vickers
microhardness and Young's modulus measurements. The Vickers
microhardness values (Shimadzu HMV-2 microdurometer) were
obtained with load of 0.200 kgf (1.961 N) and dwell time of 60 s. The
Young's modulus values (Sonelastic instrument, ATCP Physical
Engineering) were acquired by the excitation impulse method.
Damping factor of the samples was analyzed by internal friction
measurements (Q1), using a DMA50 Metravib equipment, in the
tension-compression mode, displacement of 5.106 m, with oscil-
latory frequency of 1 Hz, at room temperature. The average values
were calculated from five measurements for each sample. Me-
chanical tests followed the standard procedures for metallic ma-
terials [25,26].
3. Results and discussion
The visual plot of the pressure inside the tube during the doping
treatments and the final oxygen content of the samples are pre-
sented in Fig. 1. In Fig. 1a, a sharp decrease in the pressure is
observed in a few seconds, followed by a saturated region. The
initial abrupt decrease could be due to the natural oxide layer
growth, which was accelerated by the high temperature [15]. In the
saturated region, the pressure dropped exponentially, suggesting a
slow incorporation of oxygen atoms into the bulk. Without gas
159
Fig. 1. (a) Pressure vs. time in the doping treatment; (b) Final oxygen content.
charge (0 Torr), the curve remained constant, indicating an
adequate isolation of the experimental apparatus. However, oxygen
content did not match with the corresponding gas charge of the
doping treatments (Fig. 1b). Ti-15Zr-5Mo alloy presented the
highest value at 101 Torr, while Ti-15Zr-15Mo alloy showed a
decrease at low gas charge. Ti-15Zr-10Mo alloy did not present a
significant increase with the amount of oxygen. Ti-15Zr-7.5Mo and
Ti-15Zr-20Mo alloys exhibited a non-linear variation with the gas
charge. Overall, it can be noted the final amount of oxygen was
affected mainly by the chemical composition and also by the
crystalline structure, taking in account that Mo content change the
phase composition of Ti-15Zr-based alloys [27,28]. As example,
Schuh [29] reported an oxygen coefficient diffusion in the Ti
metallic matrix of 1.20 109 cm2/s in the a phase (hcp) and 7.13
109 cm2/s in the b phase (bcc) at 932  C. And Lu et al. [30] detected
a significant effect of the composition on the coefficient diffusion
and internal friction of Ti-Nb-X-O (X ¼ Al, Sn, Cr, and Mn), and this
effect was related to the chemical interaction of oxygen with the
substitutional elements. But, it is worth to mention that the
dependence of oxygen diffusion coefficient of Ti-based materials in
the distinct crystalline phases and its interaction with the alloying
elements are not fully understood in the literature.
The XRD patterns as a function of oxygen are illustrated in Fig. 2.
Ti-15Zr-5Mo alloy presented a combination of a” and b phases
without gas charge (0 Torr), and it had a slight variation in the
peak's intensities with the increase of oxygen. Ti-15Zr-7.5Mo alloy
exhibited b peaks with low-intense a” phase peaks, without sub-
stantial differences with the amount of oxygen. The other samples
showed only b peaks in all conditions. The XRD patterns indicated
that the level of oxygen in the samples (less than 1 wt%) was not
enough to induce a significant secondary phase precipitation. For
comparison, Nakai et al. [7] did not detect noticeable differences in
the XRD pattern of solutionized Ti-29Nb-13Ta-4.6Zr alloy with
oxygen contents of around 0.12 and 0.42 wt%. Conversely, Tahara
et al. [31] observed a precipitation of a” phase in Ti-23Nb alloy with
an oxygen content of 1 wt%. In both cases, the authors noted a
remarkable effect of oxygen content on the mechanical properties.
The Rietveld's refinement parameters of the XRD patterns are
presented in Table 1. The Rs parameters (RF2, Rwp and Rp) and Gof
indicate the level of proximity between the theoretical and exper-
imental curves. In general, Rs values less than 10% and Gof below
3.0 are considered adequate for Rietveld's refinement of XRD pat-
terns [32]. As it can be seen, the refinement parameters of the
160 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167

Fig. 2. XRD pattern as a function of oxygen.

Table 1
Rietveld's parameters for Ti-15Zr-xMo alloys.

Sample O (wt%) Gofa RF2 (%)a Rwp (%)a Rp (%)a

Ti-15Zr-5Mo 0.215 1.743 9.78 8.42 6.51

0.244 1.668 9.92 7.94 6.26
0.252 1.672 8.43 7.49 5.79
0.318 1.591 9.86 6.70 5.23
Ti-15Zr-7.5Mo 0.144 1.955 6.41 7.62 5.81
0.199 1.520 6.81 6.74 5.25
0.236 1.716 6.24 7.17 5.72
0.430 1.745 6.34 7.17 5.66
Ti-15Zr-10Mo 0.250 1.668 9.08 8.33 6.49
0.252 1.561 8.66 7.93 6.11
0.253 1.640 9.00 8.32 6.40
0.256 1.503 8.68 8.21 6.38
Ti-15Zr-15Mo 0.196 1.869 7.07 8.83 6.80
0.207 1.799 6.55 8.25 6.47
0.283 1.848 7.36 8.15 6.34
0.347 1.958 6.02 9.21 7.13
Ti-15Zr-20Mo 0.150 1.356 7.05 7.91 6.13
0.153 1.892 9.81 8.82 6.90
0.195 1.775 8.79 8.86 6.93
0.227 1.693 8.61 8.29 6.50
Fig. 3. Refined pattern of Ti-15Zr-10Mo-0.253O alloy.
a
Godness of fitness (Gof or c2); Expected residual factor (Rexp); Weighted profile
residual factor (Rwp); Parametric or Bragg residual factor (Rp).
15Zr-5Mo, Ti-15Zr-7.5Mo, and Ti-15Zr-10Mo alloys presented a
slight change in the a”/b phase proportion with the amount of
samples remained close to those in previous reports [24,33]. As an
oxygen, and Ti-15Zr-15Mo and Ti-15Zr-20Mo alloys exhibited a full
example, the visual plot of the refined Ti-15Zr-10Mo-0.253O alloy
b phase. The variation of the a”/b phase proportion can be a result
ensures the excellent fit between simulated and experimental
of the inter-diffusion of oxygen atoms between these phases,
curves of the samples (Fig. 3), which turns the calculated structural
inducing phase transformations processes [7]. As comparison, Kim
parameters and phase proportions appropriate for the study. The
et al. [34] verified a b-stabilizer action of oxygen in Ti-Nb alloys,
phase compositions as a function of oxygen are shown in Fig. 4. Ti-
which acted on the u and a” phase suppression. The effect of
 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167 161

Fig. 4. Quantitative phase analysis.

oxygen content on the b phase cell parameter is presented in Fig. 5. small decrease in the cell parameter with oxygen content, whereas
Ti-15Zr-5Mo, Ti-15Zr-7.5Mo, and Ti-15Zr-10Mo alloys showed a Ti-15Zr-15Mo and Ti-15Zr-20Mo alloys exhibited a gradual

Fig. 5. b phase crystalline parameter.

162 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167

Fig. 6. Micrographs of doped Ti-15Zr-5Mo alloy.

increase. The crystalline parameter variation in the monophasic b
type samples (Ti-15Zr-15Mo and Ti-15Zr-20Mo alloys) was due to
the oxygen atomic radius (0.06 Å), which is higher than that of the
interstitial tetrahedral and octahedral sites, producing distortion of
the crystalline structure, as observed by Martins Jr. and Grandini
[35] in b-type Ti-15Mo alloy. But, in the case of biphasic a” þ b type
samples (Ti-15Zr-5Mo, Ti-15Zr-7.5Mo and Ti-15Zr-10Mo alloys), the
cell parameter variation were oppose due to possible inter-
diffusion of oxygen between the Ti's phases, as already observed
by Nakai et al. [7].
The microstructural evolution of the samples in terms of oxygen
content is shown in Figs. 6e10. Ti-15Zr-5Mo (Fig. 6), Ti-15Zr-7.5Mo
(Fig. 7), and Ti-15Zr-10Mo (Fig. 8) alloys presented b phase grains
permeated by a” phase acicular structures. The amount of acicular
structures clearly decreased with the Mo addition but remained
uncertain with the oxygen content. Ti-15Zr-15Mo and Ti-15Zr-
20Mo alloys exhibited b phase grains with small structures near
the grain boundaries. In our previous study, we found that the
preferential diffusion of oxygen into the grain boundaries,
compared to the inter-granular region, can produce the precipita-
tion of acicular structures on these alloys [12]. It is worth to
mention that the metastable phase precipitates were induced

Fig. 7. Micrographs of doped Ti-15Zr-7.5Mo alloy.

 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167 163

Fig. 8. Micrographs of doped Ti-15Zr-10Mo alloy.

during the water quenching step of the doping treatments [36].
This feature is illustrated in Fig. 11, which shows the oxygen atoms
located preferentially in the grain boundaries along the doping
treatment and the subsequent metastable phase precipitation by
the quenching process. For comparison, Min et al. [37] observed
equiaxial b phase grains in solutionized Ti-Mo alloy with oxygen in
the range of 0.10e0.40 wt%. However, some small acicular features
of a00 phase appeared in the samples with 0.30 and 0.40 wt%O.
Conversely, Liu et al. [38] obtained only equiaxial b phase grains in
the microstructure of solutionized Ti-10Cr alloy with oxygen con-
tent between 0.06 and 0.60 wt%.
The Vickers microhardness and Young's modulus values as a
function of oxygen content are presented in Figs. 12 and 13. The
Vickers microhardness values (Fig. 12) showed a distinct depen-
dence in each alloy. Ti-15Zr-10Mo alloy did not present clear
changes with the amount of oxygen. Ti-15Zr-15Mo alloy exhibited a
slight decrease in the Vickers microhardness values, and Ti-15Zr-
5Mo, Ti-15Zr-7.5Mo, and Ti-15Zr-20Mo alloys showed a small in-
crease in values with the amount of oxygen. In the case of Ti-15Zr-
7.5Mo alloy, it is possible to observe a significative increase of
hardness with the oxygen, being also related with the suppression
of a” phase acicular structures, which are known to have lower

Fig. 9. Micrographs of doped Ti-15Zr-15Mo alloy.

164 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167

Fig. 10. Micrographs of doped Ti-15Zr-20Mo alloy.

hardness values than b phase [39]. Overall, the effect of oxygen
content on the Vickers microhardness was clearly non-linear in the
samples. Although, it is also possible to note a solid solution and
phase precipitation hardening effect in the alloys, when evaluated
in terms of the Mo content and the microstructure, in the same way
as our previous report [12]. Interstitial oxygen is well known for its
hardener effect on the Ti metallic matrix [36]. Zabler [40] studied
the strengthening effect of interstitial oxygen on Ti-6Al-4V (grade
5) and cp-Ti (grade 2), and found an increase in hardness with the
oxygen's compositional gradient. Martins Jr. et al. [15] and Vicente
et al. [14] obtained similar results in Ti-xZr (5, 10, and 15 wt%) and
Ti-15Mo alloys, in which they detected a gradual increase in
hardness with oxygen content. However, Silva et al. [18] detected a
similar non-linear dependence between hardness and oxygen
content in binary Ti-xNb (5 and 10 wt%) alloys. Regarding the
Young's modulus values (Fig. 13), it was possible to note distinct
behaviors in the samples as function of oxygen. In fact, the relation
between Young's modulus and oxygen content in Ti-based alloys is
not fully understood, as it appears to be dependent on the crys-
talline structure and alloying elements [3,41]. In terms of crystalline
structure, it is well known that the b phase has the minimal values
between the Ti's phase, while the u phase has the maximum. This
fact is clear for the Ti-15Zr-7.5Mo and Ti-15Zr-15Mo alloys for
example, the distinct values is related with the b stabilization effect
of Mo and metastable phases precipitation, as reported earlier in
our previous studies [11,12]. But in the case of oxygen, its effect on
the Young's modulus is controversial, once the element can
decrease the atomic bonding energy of the metallic matrix,
resulting in a low Young's modulus, as observed by Vicente et al.
[14] in a-type alloys. However, Nakai et al. [7] reported an increase
in Young's modulus in b-type Ti-29Nb-13Ta-4.6Zr alloy with oxy-
gen content of 0.12, 0.20, and 0.42 wt%. Liu et al. [42] also detected a
similar behavior in Ti-xCr (11 and 12 wt%) alloys with an oxygen
addition of 0.20e0.60 wt%. And finally, Kim et al. [34] found a this
same non-linear effect on 0.80 wt% of oxygen in Ti-xNb (24, 26, 28,
and 30 wt%). As a perspective of the other mechanical properties,
Fig. 14 exhibits the internal friction values of the samples as func-
tion of oxygen content at room temperature. It can be seen a clear
increase with the amount of oxygen, similarly non-linear, which
could be related to the pinning effect of the interstitial in the
metallic matrix, avoiding substitutional atomic movement and
dislocation displacement across the grains boundaries [43]. It
shows that a minimal variation in the oxygen content can alter
significantly the mechanical properties of the samples, which could
be interesting for the biomedical field.
In summary, the amount of oxygen produced a slight change in
the phase composition, crystalline structure parameters, and
microstructure, while Vickers microhardness and Young's modulus

Fig. 11. Phase precipitation model for the doping process.

D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167 165

Fig. 12. Vickers microhardness values.

Fig. 13. Young's modulus values.

166 D.R.N. Correa et al. / Journal of Alloys and Compounds 775 (2019) 158e167
Fig. 14. Internal friction as function of oxygen.
exhibited a non-linear dependency with the oxygen content.
Interstitial oxygen is expected to have an important role in the
mechanical deformation modes and protection of the metallic
surface, resulting in high mechanical strength and corrosion
resistance, as indicated before in the literature [17,44]. In this sense,
tensile and electrochemical tests can give important information
about these issues, which could be scope of further investigations.
Therefore, the use of oxygen's doping treatments can be useful to
modify the microstructure and mechanical properties of Ti alloys,
keeping the main composition unchanged. It could be very prom-
ising for metallic biomaterials, in special dental and orthopaedical
implants, where biomechanical movements and tribocorrosion
actions are constantly employed.
4. Conclusion
In this study, the crystalline structure, microstructure, and
selected mechanical properties of Ti-15Zr-xMo alloy were adjusted
by oxygen doping. The following conclusions can be made:
 Oxygen absorption was directly dependent of the composition,
crystalline structure, and microstructure of the samples;
 The amount of oxygen produced small alterations in the XRD
patterns, affecting the martensitic a” phase precipitation during
water quenching step;
 Quantitative phase analysis indicated some variations of the a”/
b proportion with the oxygen content related to the interstitial
oxygen diffusion between the phases;
 The b phase crystalline parameter was sensitive to the amount
of oxygen in a non-linear manner;
 The Vickers microhardness, Young's modulus and internal fric-
tion values were affected differently by the amount of oxygen
through different effects, such as solid solution hardening,
distortion of crystalline structure, bonding energy variation and
pinning process;
 The amount of oxygen incorporated by the doping treatment
showed its potential to be used in biomedical Ti-15Zr-xMo al-
loys once it produced small changes in the microstructure and
mechanical properties, keeping the main composition
unaltered.
Acknowledgments
The authors would like to thank the Physics Department of the
School of Sciences (UNESP), for the XRD and SEM measurements,
and the reviewers for their valuable comments. This study was
supported by the following funding agencies: FAPESP (grants
#2010/20440-7 and #2015/00851-6) and CNPq (grants #207417/
2015-6 and #307279/2013-8).
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