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Electrochimica Acta 53 (2008) 2809–2817

Effects of Zr content on microstructure and corrosion resistance of

Ti–30Nb–Zr casting alloys for biomedical applications
Danielle Q. Martins, Wislei R. Osório, Maria E.P. Souza, Rubens Caram, Amauri Garcia ∗
Department of Materials Engineering, State University of Campinas, UNICAMP, P.O. Box 6122, 13083-970 Campinas, SP, Brazil
Received 3 September 2007; received in revised form 24 October 2007; accepted 24 October 2007
Available online 4 November 2007

Abstract
Titanium alloys show attractive properties for biomedical applications where the most important factors are biocompatibility, corrosion resistance,
low modulus of elasticity, very good strength-to-weight ratio, reasonable formability and osseointegration. The aim of this study was to investigate
the effects of Zr content (7.5 and 15 wt%) on microstructure and corrosion resistance of Ti–30Nb–Zr as-cast alloy samples. The corrosion tests
were carried out in a 0.9% NaCl (0.15 mol L−1 ) solution at 25 ◦ C and neutral pH range. A horizontal centrifuged solidification set-up was used
to obtain as-cast samples with a fine dendritic arrangement. In order to evaluate the corrosion behavior, electrochemical impedance spectroscopy
(EIS), polarization curves and an equivalent circuit analysis were used. It was found that the as-cast microstructure tends to have the dendrite arm
spacings reduced with increasing Zr content. The results have shown that the addition of Zr to a Ti–30Nb alloy has been efficient to stabilize the
beta phase. The resulting impedance parameters and passive current densities have shown that the Ti–30Nb alloys sample without Zr addition
presents a higher surface reactivity which can induce a better osseointegration than those containing Zr.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Ti–Nb alloys; Centrifugal casting; ElS; Bone ingrowth; Osseointegration

1. Introduction strength increases and the elongation decreases with increasing

Titanium alloys are among the most studied metallic bioma-
terials, particularly those with vanadium- and aluminum-free
Ti alloys since these elements exhibit high cytotoxicity and
negative tissue response in vivo and may induce senile demen-
tia, neurological disorders and allergic reactions [1–4]. It is
well known that recent biomaterials research has focused on ␤-
titanium alloys due to increased biocompatibility and decreased
Young’s modulus. The former provides biological acceptance of
the implant by the body and the latter promotes a load sharing
between the implant and natural bone [4,5]. Some studies have
shown that Ti–Nb alloys ranging from 20 to 50 wt% Nb exhibit
a modulus of elasticity of about 60 GPa [5–7], which is closer
to that of bone when compared to those of other conventional
alloys applied to orthopedic implants. The increase on Nb con-
tent tends to decrease the modulus of elasticity and stabilizes
the ␤-titanium phase. It has also been reported that the yield
∗ Corresponding author. Tel.: +55 19 3521 3320; fax: +55 19 3289 3722.
E-mail address: amaurig@fem.unicamp.br (A. Garcia).
Nb content [8].
The Ti–35Nb–7Zr–5Ta alloy has a lower modulus of elastic-
ity (55 GPa) than other metallic alloys typically used for implant
components [5,8–11]. This alloy is a ␤-type titanium alloy with
non-toxic and non-allergic elements, which can be considered to
be one of the best choices for orthopedic implants [5,8]. Ti–Nb
alloys have presented superior corrosion resistance when com-
pared to the traditional Ti–6Al–4V alloy [12]. Uniform surface
corrosion of Ti–Nb alloys provides a passive film which can be
formed by ␣-Ti2 O3 , TiO2 and Nb2 O5 [13–15].
The high cost of titanium goods is not only due to the price
of raw titanium but, mainly due to fabrication processes. An
approach to reduce cost may be found by applying Ti alloy cast-
ing processes, especially when complex shapes are necessary.
It is well known that the resulting microstructure of metal-
lic alloys has an important role on mechanical properties and
corrosion behavior of as-cast components [16–19]. Generally,
fine-structure castings are desirable since smaller grain size
enhances mechanical strength and toughness, the microstructure
and general properties are more isotropic and species segregation
is reduced. In this work, a refined microstructure was obtained

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.10.060
2810 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817
by using a centrifuged casting process in a massive copper cru-
cible. The centrifugal force favors the thermal contact between
molten metal and mold wall and promotes a copious nucleation
of grains which will lead to a fine equiaxed structure. On the
other hand, as far as the corrosion resistance of metallic alloys
is concerned, it is also very important to analyze the dendritic
scale inside the grains, the solute distribution in the interden-
dritic region and the anodic/cathodic behavior of the segregated
solute with respect to the dendritic matrix [20]. The centrifuged
casting process can provide two different structures: a ‘band-
ing’ structure (in which the special structural discontinuity is
featured) or a typical structure that usually contains a chill zone,
a columnar zone and a central equiaxed zone [21].
The aim of this study was to investigate the effects of Zr
content (7.5 and 15 wt%) on the resulting microstructure and on
the electrochemical corrosion behavior of Ti–30 wt% Nb as-cast
alloy samples in a 0.9% NaCl (0.15 mol L−1 ) solution at 25 ◦ C
and a neutral pH range.
2. Experimental procedure
Ti–30Nb and Ti–30Nb–Zr alloy samples were prepared from
commercially pure metals: Ti (99.86 wt%), Nb (99.99 wt%) and
Zr (99.99%). Ti–30Nb–Zr alloys with two different Zr contents
(7.5 wt% Zr and 15 wt% Zr) were melted in an arc-melting
furnace with a non-consumable tungsten electrode and water-
cooled copper hearth under an ultra-pure argon atmosphere.
Initially, vacuum of 10−3 atm was created and then ultra-pure
argon was injected. In order to homogenize the sample compo-
sition, at least five remelting steps were carried out and in each
operation the sample was slipped into the hearth. In all cases,
argon atmosphere and slight vacuum conditions were employed.
This procedure guarantees the minimization of undesirable oxi-
dation. More details about the experimental procedure can be
found in a previous article [22].
The centrifuged casting set-up consists of a permanent cop-
per mold and a copper crucible positioned in a centrifugal arm,
which rotates around a central axis, as shown in Fig. 1. A 30 g
sample is arc-melted and the homogenized alloy sample is posi-
tioned at the crucible and remelted in situ. After, it is immediately
injected into a permanent copper mold by the centrifugal force
by using a rotation of about 1000 rpm.
The resulting ingots were sectioned, ground by using silicon
carbide papers up to 1200 mesh, polished and etched to reveal the
microstructure (Kroll’s etchant 5 mL of HF, 30 mL of HNO3 and
Fig. 1. Schematic representation of the centrifuged casting set-up.
65 mL of H2 O). Microstructural characterization was performed
by applying optical microscopy (Olympus BX60M) and SEM
(JMS T20 of Jeol Co., Japan). X-ray diffraction patterns were
obtained utilizing a Rigaku diffractometer (DMAX 2200) oper-
ated at 40 kV and 30 mA with Cu K␣ radiation and a wavelength,
λ, of 0.15406 nm.
Electrochemical impedance spectroscopy (EIS) tests were
carried out in samples extracted from the centrifugally solid-
ified ingots by using a solution of 0.9% NaCl (0.15 mol L−1 )
at 25 ◦ C under a neutral pH range (of about 6.80). Such solu-
tion was used to simulate the human body fluid [13,14]. EIS
measurements began after an initial delay of 30 min for the sam-
ple to reach a steady-state condition. A potentiostat coupled to
a frequency analyzer system, a glass corrosion cell kit with a
platinum counter-electrode and a saturated calomel reference
electrode (SCE) were used to perform the EIS test. The work-
ing electrodes consisted of Ti–30Nb–Zr alloy samples which
were positioned at the glass corrosion cell kit, leaving a circu-
lar 0.33 cm2 metal surface in contact with the electrolyte. The
potential amplitude was set to 10 mV in open-circuit potential
and the frequency range was set from 10 mHz to 100 kHz.
Potentiodynamic measurements were also carried out in a
0.9% NaCl solution at 25 ◦ C using a potentiostat at the same
positions where the afore-mentioned EIS tests were carried out.
These tests were conducted by stepping the potential using a
scanning rate of 10 mV/s from −0.800 mV (SCE) to +3000 mV
(SCE). Using an automatic data acquisition system, the poten-
tiodynamic polarization curves were plotted and both corrosion
rate and potential were estimated by Tafel plots by using both
anodic and cathodic branches. Duplicate tests for EIS and poten-
tiodynamic polarization curves were carried out. In order to
supply quantitative support for discussions of these experimen-
tal EIS results, an appropriate model (ZView® version 2.1b) for
equivalent circuit quantification has also been used.
3. Results and discussion
3.1. Microstructures
Typical optical micrographs of the alloys experimentally
examined are shown in Fig. 2. It can be seen that the cen-
trifuged casting process has induced a fine dendritic pattern
due to the inherent high cooling rates during solidification.
It can also be observed that the addition of Zr has a strong
refinement effect on the secondary dendrite arm spacing which
decreases significantly as the Zr content is increased. As previ-
ously mentioned, the centrifuged casting increases the number
of nucleation sites and hence fine equiaxed grains are obtained.
The final microstructure is then constituted by fine equiaxed
grains, in which the fineness of the dendritic pattern is associ-
ated not only with the high cooling rate of the centrifuged casting
process but also with the Zr content of the alloy. Generally,
both mechanical and fatigue properties increase with centrifuged
casting applications [23].
The final microstructure, immediately after solidification in
the centrifuged apparatus will be formed by a dendritic array
where the dendritic matrix is formed by a Nb-rich phase with
 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817 2811

Fig. 2. Typical microstructures of Ti–30 wt% Nb–Zr alloys centrifuged cast: (a) 0 wt% Zr, (b) 7.5 wt% Zr and (c) 15 wt% Zr.

Ti-rich phases located in the interdendritic region (orthorhom- mined by ultrasonic methods [16]. The higher Young’s modulus
bic ␣ martensite and ␻ athermal phases) since Nb distribution for the Ti–30Nb alloy can be attributed to the ␻-phase precipi-
coefficient is bigger than unity. In Fig. 2(a), the light region tation.
is associated with the Nb-rich dendritic matrix and the dark
region is the interdendritic Ti-rich solution with a secondary 3.2. EIS measurements and equivalent circuit analysis
dendritic arm spacing (λ2 ) of about 29 ␮m. The addition of Zr
strongly reduces λ2 : 12 and 5 ␮m for the Ti–30Nb–7.5Zr and In order to analyze the effects of Zr content on the general
Ti–30Nb–15Zr alloy samples, respectively, as shown in Fig. 2(b) (uniform) corrosion resistance of the Ti–30Nb–Zr centrifuged
and (c). Dendrite arm spacings are of high importance, since cast samples, EIS diagrams and polarization tests were carried
they affect not only the mechanical properties and corrosion
resistance of castings but also the subsequent manufacturing of
components from ingots [17–19,23].
Fig. 3 shows typical X-ray diffraction patterns (XRD) of
Ti–30Nb, Ti–30Nb–7.5Zr and Ti–30Nb–15Zr alloy samples.
Besides the typical dendrite array of the Ti–30Nb alloy, a fine
acicular ␣ martensitic phase is clearly observed throughout the
interdendritic regions. Further, a slight precipitation of the ␻-
phase has been detected in the XRD patterns, as shown in Fig. 3.
The literature reports that the amount of ␣ -phase increases with
increasing cooling rate due to the transformation of ␤-phase into
␣ [16,24,25]. On the other hand, only ␤-phase peaks have been
detected for the Ti–30Nb–Zr alloys, as shown in Fig. 3. This rein-
forces the effect of zirconium as a ␤-phase stabilizer element in
Ti alloys [2,3,16]. It is well known that ␤-type Ti–Nb based
alloys have reduced Young’s modulus. For the alloys exam-
ined in the present investigation, the Young’s modulus is about
100 GPa for theTi–30Nb alloy, while for those Zr-containing Fig. 3. X-ray diffraction (XRD) patterns for Ti–30Nb–15Zr, Ti–30Nb–7.5Zr
alloys it lies between 60 and 70 GPa. These values were deter- and Ti–30Nb alloy samples.
2812 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817

Fig. 4. Experimental and simulated EIS diagrams obtained by the ZView® software for: (a) Ti–30Nb, (b) Ti–30Nb–7.5Zr and (c) Ti–30Nb–15Zr alloys in a 0.9%
NaCl solution at 25 ◦ C.

out in a 0.9% NaCl solution. Fig. 5 shows experimental and
simulated EIS diagram results for Ti–30Nb, Ti–30Nb–7.5 and
Ti–30Nb–15Zr alloy samples.
It can be seen in Fig. 4, that the moduli of impedance (Z)
for those Zr-containing Ti–Nb alloys are higher than that of the
Ti–30Nb alloy. These qualitative results and other impedance
parameters shown in Table 1 (capacitances and resistances) are
indicative of a nobler electrochemical behavior of Ti–Nb alloys
with Zr addition. The impedance parameters supply quantitative
support for discussions of EIS results and were obtained by the
ZView® software, by adopting the well known equivalent circuit
initially proposed by Pan et al. and other researchers [26–30],
as shown in Fig. 5.
The agreement between experimental and simulated results
indicates that the experimental results are well fitted to the pro-
posed equivalent circuit. The fitting quality was evaluated by
chi-squared (χ2 ) [20,26] values of about 10−4 , as shown in
Table 1.
The physical significance of the elements of the proposed
equivalent circuit has been intensively reported in the literature
[20,24–30]. The model assumes that the oxide layer on the three
Ti alloys experimentally examined consists of a barrier-like inner
layer and a porous outer layer. In this model, Rel corresponds to
the resistance of the electrolyte (0.9% NaCl solution) which in
Bode diagram is expressed in a high frequency limit (F > 1 Hz).
R1 and R2 are the resistances of porous and barrier layers [24–29]
which are associated to the charge transfer resistance through the
porous layer and the participation of adsorbed intermediates.
ZCPE(1) corresponds to the capacitance of the porous layer and
ZCPE(2) to the capacitance of the barrier layer which seem to
 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817
Table 1
Impedance parameters for Ti–30Nb and Ti–30Nb–xZr centrifuged cast alloys
Parameters Ti–30Nb
Rel( cm−2 ) 159.7
ZCPE(1) (106  s−n cm2 ) 15.94 (±1.9)
ZCPE(2) (106  s−n cm2 ) 18.02 (±2.1)
n1 0.95
n2 0.81
R1 ( cm−2 ) (porous) 0.4 × 103
R2 ( cm−2 ) (barrier) 1.26 × 106
χ2 10 × 10−4
Error results from fitting the experimental data in the equivalent circuit analysis.
be associated to the double layer formation. A constant-phase
element representing a shift from an ideal capacitor was used
instead of the capacitance itself, for simplicity. The impedance
of a phase element is defined as ZCPE = [C (jω)n ]−1 , where C is
the capacitance, ω is the frequency and −1 ≤ n ≤ 1. The value
of n seems to be associated with the non-uniform distribution of
current as a result of roughness and surface defects [26].
Comparing the capacitances ZCPE(1) and ZCPE(2) for Ti–30Nb,
Ti–30Nb–7.5Zr and Ti–30Nb–15Zr alloys samples, it is possible
to observe that the Ti–30Nb alloy has the highest capaci-
tances (ZCPE(1) and ZCPE(2) of about 16 106  s−n cm2 or 16
and 18 ␮F cm−2 , respectively) when compared with those of the
Ti–Nb–Zr alloys. On the other hand, the polarization resistances
of the inner barrier layer (R2 ) for all three alloys are signifi-
cantly higher than R1 (porous layers). This indicates that the
protection is predominantly provided by the inner barrier layer,
as also observed by Assis et al. for Ti-alloys [26]. The ZCPE(2)
values must be analyzed with association with the R2 values. It
seems that the component ZCPE(2) is responsible for very high
phase angles obtained at low frequencies. For the Ti–30Nb alloy
sample, ZCPE(1) and ZCPE(2) are similar (of about 20 ␮F cm−2 );
however, the barrier layer resistance (R2 ) is superior by a fac-
tor of about 103 times. For the Ti–30Nb alloy sample with Zr
additions, the capacitance of the porous layer (ZCPE(1) ) is higher
than the barrier one (ZCPE(2) ) by a factor of about 2–20 times.
A similar behavior has also been recently reported in the lit-
erature [26]. Low capacitances can be associated with both an
increase of the passive layer thickness [28,29] and a decrease
of the oxide film dielectric constant (due to variation in ratio of
the electrolytic solution volume/oxide film) [30]. Low capaci-
tances associated to high polarization resistances are conducive
to a nobler electrochemical corrosion behavior [20,27,28]. Thus,
Fig. 5. Proposed equivalent circuit for modeling impedance parameters for
Ti–Nb and Ti–Nb–Zr alloy samples in a 0.9% NaCl solution.
2813
Ti–30Nb–7.5Zr Ti–30Nb–15Zr
170.8 169.4
10.55 (±0.8) 7.44(±0.3)
0.98 (±0.3) 2.61 (±0.2)
0.89 0.89
0.96 0.66
7.6 × 103 27 103
2.15 × 106 2.35 × 106
9.7 × 10−4 19 × 10−4
the impedance parameters shown in Table 1 permit to con-
clude that the addition of Zr to a centrifuged cast Ti–30Nb alloy
increases the corrosion resistance in a 0.9% NaCl solution. In the
present investigation, zirconium has shown to provide a nobler
characteristic to the alloy. It has also favored the ␤-phase stabi-
lization and has provided a refinement of the dendritic network.
It seems that the synthesis of such factors has been responsi-
ble for the resulting better corrosion resistance of Ti–30Nb–Zr
alloys.
3.3. Polarization results
Fig. 6 shows experimental polarization curves in a 0.9% NaCl
solution, for the three studied alloys. The corrosion current den-
sities (ICorr ) were obtained from the polarization curves by Tafel
plots using both cathodic and anodic branches of the polar-
ization curves. Such results reinforce the corrosion resistance
tendency favoring the Ti–30Nb centrifuged cast alloys with Zr
additions. It can be seen that ICorr decreases with increasing Zr
content, with the highest ICorr being observed for the Ti–30Nb
alloy.
A partial stabilization on the current density is observed
between 2 and 3 × 10−8 A cm−2 for all the three studied alloys
which is associated to an oxide film formation. However, this
oxide film becomes more stable of about 0.1 V for all the three
alloys. Different passive current densities (IPP ) are associated
to such corrosion potential for each alloy. In Fig. 6, the highest
IPP is exhibited by the Ti–30Nb alloy (of about 15 ␮A cm−2 ),
the intermediate value is that of the Ti–30Nb–7.5Zr (of about
7 ␮A cm−2 ), and the lowest that of the Ti–30Nb–15Zr alloy
(of about 3.5 ␮A cm−2 ). The association of values of IPP ,
ICorr and impedance parameters permits to conclude that the
Ti–30Nb–15Zr alloy has a nobler electrochemical corrosion
behavior when compared with those of the other examined
alloys.
At potentials of about 1300, 1700 and 2300 mV (SCE),
occurrence of passive film breakdown can be observed for the
Ti–30Nb–15Zr, the Ti–30Nb–7.5Zr and the Ti–30Nb casting
alloys, respectively. Although very protective Ti oxide films are
formed on the surface of such centrifuged cast samples, the high
values of IPP indicate that defects in the oxide film can be formed,
i.e., there is a tendency of more irregular or porous oxide layer
formation [26].
2814 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817
Fig. 6. (a) Experimental polarization curves for Ti–30Nb, Ti–30Nb–7.5Zr and
Ti–30Nb–15Zr centrifuged cast samples in a 0.9% NaCl solution at 25 ◦ C and
(b) magnification evidencing the breakdown potential occurrence.
The development of a stable bone-implant interface is crit-
ical to the successful use of orthopedic and dental prostheses.
Several approaches have been developed to stimulate favorable
host-implant interactions, such as creating implant surfaces with
macroscopic irregularities, porous surfaces, and osteoconduc-
tive coatings (e.g. hydroxyapatite or similar calcium phosphate
coatings) [31]. Biological advantages of texture surfaces might
be gained by the capacity of these surfaces to create a microme-
chanical anchorage with bone interlocking, which turns out to
be a stronger implant fixation than for smooth surfaces. Bone
interlocking requires the conjunction of a minimal roughness
with peaks and/or valleys of adequate shape that permit bone
ingrowth and bone retention [31,32].
Since biocompatibility, good corrosion and mechanical resis-
tances, very good strength and low modulus of elasticity are
recognized as intrinsic characteristics of Ti-Nb alloys, the con-
trol of surfaces with more porous aspect can be very useful
for planning both micromechanical anchorage between bone-
implant and ingrowth of the bone in order to achieve long-life
implantation. In the present investigation, the results of corro-
sion tests have indicated that, although Zr content significantly
increases the electrochemical performance of centrifuged cast
Ti–Nb based alloys [13], the Ti–30Nb alloy samples has exhib-
ited an oxide film which is more irregular if compared to that of
the other Ti–Nb–Zr alloys. This can be an important factor for
the improvement of osseointegration.
By analyzing the resulting microstructures before and after
corrosion tests, it seems that the refinement of the dendrite
arm spacing, which has been associated with Zr additions, has
strongly influenced the oxide film formation for both Ti–30Nb
and Ti–30Nb–xZr alloy samples. Experimental results of the
electrochemical corrosion behavior permit to affirm that finer
secondary dendritic arm spacings induce better corrosion behav-
ior than coarser ones. From the electrochemical point of view,
the Ti-rich regions have nobler corrosion behavior when com-
pared with Nb-rich regions. Thus, Ti–30Nb alloys immersed
in some aggressive environment have the Ti- and Zr-rich
regions (interdendritic regions) acting as anodic protective bar-
riers “enveloping” the Nb-rich dendritic matrix. On the other
hand, there is a cathodic protection in Nb-rich regions. Thus,
finer dendritic structures with a consequent more homogeneous
distribution of the nobler region along grain boundaries and
interdendritic regions will exhibit a more homogeneous oxide
film with a consequent improvement on the corrosion resistance
than coarser dendritic structures. Fig. 7 shows typical SEM
images of the resulting surface oxide films after polarization
cycles in a 0.9 M NaCl solution for Ti–30Nb and Ti–30Nb–15Zr
alloys. It is clearly observed that the presence of Zr has pro-
vided a more homogeneous oxide film which is associated to
the impedance parameters results afore-mentioned. On the other
hand, a non-homogeneous oxide layer is developed at the surface
of the Ti–30Nb alloy sample.
The impedance parameters shown in Table 1, specifically,
capacitances and polarization resistances of both outer porous
and inner barrier layers have important roles to the understanding
of the kinetics of oxide film formation and its electrochemical
behavior. The literature proposes a schematic representation for
inner barrier and outer porous layer lattices, as shown in Fig. 8(a)
[24–30]. A number of procedures can be used to prepare the
surface texture of an implant component such as acid exposi-
tion, subsequent thermal or electrochemical treatments and some
biocompatible coatings application. The former depends on the
exposure time, nature and composition of the used acid which
does not create a common topography and in industrial process
is not fully reproduced [33]. The latter depends on the previ-
ously formed oxide film when a spray surface coating technique
is used.
It has been recently reported [30] that the anodizing treat-
ment in a HF solution can produce both inner and outer oxide
layers with porous aspect, increasing the inner layer corrosion
resistance. In order to propose a mechanism for dual-oxide
porous layer formation, some modification on the schematic
representation of Fig. 8(a) is made, as shown in Fig. 8(b). In
despite of the proposed modification, the interpretation of the
previous proposed equivalent circuit is the same. It is well
known that an electrolytic solution can reside into the porous
 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817 2815

Fig. 7. Typical SEM images of surface oxide film formed after polarization cycle in the Ti–30Nb and Ti–30Nb–15Zr alloy samples.

vacancies of the oxide layer. This can modify the oxide film
dielectric constant and its thickness, and as a direct consequence,
can modify the resulting capacitances (ZCPE ) and polarization
resistances (R).
The literature reports that small pores (Fig. 8b and d) decrease
the capacitance due to a decrease of the film dielectric constant or
when the oxide film thickness is increased [29,30]. It is suggested
that the barrier layer thickness can be significantly increased due
to the associated reactions between metastable oxide particles,
e.g. Ti2 O3 and Nb2 O5 [14,15] (resident in the outer layer) and
the electrolytic solution. As a consequence, some oxide particles
of the outer layer are transformed in more stable oxide particles
and due to electronic and nature affinities (e.g., particle size and
geometry) they are incorporated into the inner layer providing
a finer porous layer. Associated to such mechanism, the inner
layer can have its capacitance increased while the outer layer
capacitance is not necessarily modified.
The experimental and simulated EIS results and the result-
ing oxide films shown in Fig. 7 give support to the proposed
mechanism. The centrifuged casting process and the addition
of a nobler solute to the Ti–30Nb alloy can be used as alter-
native ways to produce components with better characteristics
for medical implants. The former induces the formation of fine
equiaxed grains and influences the resulting dendritic array and
the latter affects the refinement of the dendritic microstructure
and favors ␤-phase stabilization.
Although both in vivo and in vitro tests have not been
performed to evaluate the practicability of biocompatibility
or osseointegration by using the studied Ti–30Nb alloy sam-
ples, the presented experimental corrosion tests carried out in

Fig. 8. Schematic representation of the dual-oxide layer: (a) inner barrier and outer porous layers and (b) variation of these dual-oxide layers.
2816 D.Q. Martins et al. / Electrochimica Acta 53 (2008) 2809–2817
a saline solution can be useful to demonstrate the potential of
Ti–30Nb–Zr alloy samples in biomedical applications. A recent
study [34] has reported that electrochemical tests carried out in
a Ti–Nb–Zr alloy after 410 days of immersion in a Hank’s solu-
tion has indicated a high corrosion resistance and both resistance
and capacitance values have shown a propensity to stabiliza-
tion after 3 days. Although the electrochemical tests carried out
in the present study refers to a 30 min period of immersion,
it is believed that the mechanism of oxide film formation and
growth after longer immersion periods will also be significantly
dependent on the dendritic arrangement, since the microstruc-
tural pattern and the species distribution are defined previously
during the alloy solidification.
4. Conclusions
The following main conclusions can be drawn from the
present investigation:
1. Although the centrifuged casting has induced a finer
microstructure favoring the mechanical properties, it was ver-
ified that Zr additions to the Ti–30Nb alloy has provided a
considerable refinement on the dendritic array and has pro-
vided ␤-phase stabilization (7.5Zr and 15Zr). Finer dendritic
structures with a consequent more homogeneous distribution
of the nobler region (Ti-rich region) will provide barrier pro-
tection along the grain boundaries and interdendritic regions
and will exhibit a more homogeneous oxide film with a con-
sequent improvement on the corrosion resistance than coarser
dendritic structures.
2. The experimental electrochemical results have shown that the
centrifuged cast alloy samples present a passive oxide layer
which can have a significant effect on biocompatibility. This
is a potential indication that the centrifuged casting process
is a prospective resource for the manufacturing of implant
devices.
3. The experimental EIS diagrams, polarization curves and
the equivalent circuit parameters have shown that Zr addi-
tions have improved the electrochemical corrosion behavior
of the Ti–30Nb alloy. In contrast, the Ti–30Nb cen-
trifuged cast alloy sample has a higher surface reactivity
which can induce a better osseointegration capacity when
compared to those of Ti–30Nb–Zr alloys. However, in
vivo and in vitro tests are necessary to evaluate the
real biocompatibility or osseointegration capability of such
Ti-alloys.
4. A mechanism in which the barrier layer thickness can be sig-
nificantly increased due to the associated reactions between
metastable oxide particles and the electrolytic solution has
been proposed. As a consequence, some oxide particles of
the outer layer are transformed in more stable oxide particles
and due to electronic and nature affinities they are incorpo-
rated into the inner layer providing a finer porous layer. Ti–Nb
alloy samples are composed of a dual-layer oxide consisting
of an inner barrier responsible for the corrosion protection,
and an outer porous layer which apparently facilitates the
osseointegration.
5. The centrifuged casting process and the addition of a nobler
solute to the Ti–30Nb alloy can be used as alternative ways to
produce components with better characteristics for medical
implants, i.e., with improved corrosion resistance, biocom-
patibility and osseointegration.
Acknowledgements
The authors acknowledge financial support provided by
FAPESP (The Scientific Research Foundation of the State of São
Paulo, Brazil), FAEPEX- UNICAMP and CNPq (The Brazilian
Research Council).
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