Electrochimica Acta 52 (2006) 839846

Corrosion behaviour of Ti6Al7Nb and Ti6Al4V ELI alloys

in the simulated body fluid solution by electrochemical
impedance spectroscopy
S. Tamilselvi, V. Raman, N. Rajendran
Department of Applied Sciences and Humanities, MIT campus, Anna University, Chennai 600 044, India
Received 13 January 2006; received in revised form 6 June 2006; accepted 20 June 2006
Available online 17 August 2006

Abstract
The corrosion behaviour of Ti6Al7Nb and Ti6Al4V ELI (extra low interstitial) was investigated as a function of immersion hours in
simulated body fluid (SBF) condition, utilizing potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques.
Polarisation experiments were conducted after 0, 120, 240 and 360 h of immersion in SBF solution. From the polarisation curves, very low current
densities were obtained for Ti6Al7Nb alloy compared to Ti6Al4V ELI, indicating a formation of stable passive layer. Impedance spectra were
represented in the form of Bode plots and it was fitted using a non-linear least square (NLLS) fitting procedure, in which it exhibited a two time
constant system suggesting the formation of two layers. The surface morphology of the titanium alloys have been characterized by SEM and EDAX
measurements.
2006 Elsevier Ltd. All rights reserved.

Keywords: Titanium alloys; Corrosion; Polarisation; Electrochemical impedance studies; Simulated body fluid solution

1. Introduction [5]. In vitro studies have shown a difference in cellular behaviour

Titanium and its alloys are presently used as implant mate-
rials for biomedical and dental applications. This is due to the
formation of a passive film on their surface, consisting mainly
of amorphous titanium dioxide (TiO2 ), which is responsible
for both their corrosion resistance and their biocompatibility
[1,2]. The contact between the metallic implant and the receiving
living tissues is made through the oxide layer on the implant sur-
face, which allows the ossteointegration process [3]. Ti6Al4V
is the most frequently used titanium alloy for medical implants,
however, there are still many unsolved questions regarding the
effect of its alloying components. Although the Ti6Al4V alloy
exhibit excellent corrosion properties, the metal ions released
by corrosion or wear processes may induce aseptic loosening
after long-term implantation. The Ti6Al6Nb alloy was devel-
oped [4] with mechanical properties comparable to those of high
strength Ti6Al4V, in addition with better corrosion resistance
Corresponding author. Tel.: +91 44 2223 7276; fax: +91 44 2223 2403.
E-mail address: nrajendran@annauniv.edu (N. Rajendran).
in the presence of debris generated by the wear of Ti6Al4V
and Ti6Al6Nb alloys [6].
Electrochemical behaviour of titanium and its alloys has
been reported based on biocompatibility in various physiolog-
ical mediums. Pan et al. [7] investigated the electrochemical
behaviour of commercially pure titanium in phosphate-buffered
saline solution without and with H2 O2 additions. Gonzalez
and Mirza Rosca [2] performed EIS tests of titanium and sev-
eral of its alloys (Ti10Mo, Ti10Al10Mo, Ti5Al15Mo,
Ti5Al4.5V and Ti5Al2.5Fe) in Ringer solution. Silva et al.
[8] carried out electrochemical characterization of oxide films
formed on Ti6Al4V alloy implanted with Ir in phosphate-
buffered saline solution. There are few reports describing the
electrochemical process on the alloy during the growth of
hydroxyapatite.
In the present work, EIS measurements were carried out
in order to understand the nature and growth pattern of the
films formed at different time durations in SBF solution. The
hydroxyapatite growth resulting from the immersion of spec-
imens in SBF solution was confirmed by SEM and EDAX
results.

0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.06.018
840 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846

2. Methods and materials Table 2

Chemical composition of SBF solution
2.1. Composition of titanium alloys and SBF solution Reagent Composition (g/l)

NaCl 8.00
Table 1 shows the composition of Ti6Al7Nb and Ti6Al KCl 0.40
4V ELI alloys examined in the present investigation. In order to CaCl2 0.18
simulate the physiological conditions of the human body, SBF NaHCO3 0.35
solution was used for in vitro corrosion studies and its chemical Na2 HPO4 2H2 O 0.48
MgCl2 6H2 O 0.10
composition is given in Table 2. The pH of the electrolyte was KH2 PO4 0.06
adjusted to 7.4 and temperature was maintained at 37 C. MgSO4 7H2 O 0.10
Fresh solution was used for each experiment. The titanium Glucose 1.00
samples were cut into 1 cm2 size and a brass nut was attached to
each specimens using conductive paint to ensure electrical con-
ductivity. The assembly was then embedded into an epoxy resin parameters electrolyte resistance, cell geometry, impedance of
disk. Then the samples were ground with SiC abrasive paper the conductors and the reference electrode. The intermediate fre-
up to 1000 grit, final polishing was done with 1 m diamond quency region (103 to 10 Hz) has the maximum phase angle and
paste. The samples were degreased with methanol followed by the log|Z| versus log f slope approaching 1. Those impedance
ultrasonic cleaning with deionized water. responses correspond to the capacitive behaviour of the elec-
trode and describe the dielectric properties of the electronically
2.2. Potentiodynamic polarisation studies conducting surface film. The low frequency region (f < 10 Hz)
detects the electron charge transfer process, the mass transfer
Potentiodynamic polarisation studies were carried out at 0, (diffusion or migration) processes, or other relaxation processes
120, 240 and 360 h of immersion in SBF solution for titanium taking place at the filmelectrolyte interface or within the pores
alloys. All the potential measurements were carried out with of the surface film.
reference to a saturated calomel electrode (SCE). The counter
electrode employed for the potentiodynamic polarisation studies 2.4. SEM and EDAX studies
was a platinum foil and the potentials were scanned at a rate of
0.167 mV/s in an aerated medium. Potentiostat (model PGSTAT The substrates were soaked in SBF solution for 360 h at 37 C,
12 with FRA, Autolab, The Netherlands B.V.) controlled by a then removed, washed with acetone and dried in a clean bench.
personal computer with dedicated software (GPES version 6.0) The surface morphology of the alloy and its composition before
was used for conducting the polarisation experiments. In order to and after immersion for 360 h were carried out using JSM-840A
obtain reliable results, polarisation experiments were triplicated scanning electron microscope JOEL-Japan, Link ISIS, Oxford
in SBF solution. instrument, UK in conjugation with an energy dispersive X-ray
analysis (EDAX).
2.3. Electrochemical impedance spectroscopic (EIS)
studies 3. Results and discussion

EIS studies were carried out at open circuit potential using an
electrochemical system Frequency Response Analyser (FRA),
which included a potentiostat model PGSTAT 12. Titanium spec-
imens with an exposed surface area of 1 cm2 were used as the
working electrode. The impedance spectra were acquired in the
frequency range of 104 to 102 Hz with a 10 mV amplitude sine
wave generated by a frequency response analyzer. Nyquist and
Bode plots were obtained after the specimens were immersed in
the test solution for different hours (0, 120, 240 and 360 h). Gen-
erally, three frequency regions referring to the high, intermediate
and low frequency values are obtained from impedance spectra.
This high frequency plateau of the |Z| values at f > 104 Hz, with
the phase angle approaching 0, yields the value of the electrode
ohmic or solution resistance, Rs , which includes the following
Table 1
Composition of titanium alloys
Titanium alloys Al V Nb O C
3.1. Potentiodynamic polarisation studies
The potentiodynamic polarisation studies were carried out
at 0, 120, 240 and 360 h for Ti6Al7Nb and Ti6Al4V ELI
alloys immersed in SBF solution and the results are shown
in Fig. 1a and b. The corrosion potential (Ecorr ), observed for
Ti6Al7Nb alloy was 0.428 V at 0 h, 0.400 V at 120 h,
0.359 V at 240 h and 0.289 V at 360 h. The corrosion cur-
rent density (Icorr ) observed at 0 h was 5.02 and 0.01 A cm2 at
360 h. It was observed that the Icorr decreased and Ecorr increased
towards positive direction for Ti6Al7Nb alloy from 0 to 360 h.
From the polarisation curve, as the immersion period increases
the alloy showed a stable surface film. For instance, the alloy
immersed for 360 h exhibited a very low Icorr value and also
N H Ni Fe Ta S Si Ti

Ti6Al7Nb 5.85 0.01 6.95 0.170 0.001 0.01 0.0030 0.01 0.200 0.05 0.0008 0.63 Balance
Ti6Al4V ELI 6.42 4.19 0.101 0.011 0.0052 0.198 Balance
 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846
Fig. 1. Potentiodynamic polarisation curves of titanium alloy at different immer-
sion hours in SBF solution: (a) Ti6Al7Nb and (b) Ti6Al4V ELI alloys.
a positive shift in Ecorr . A similar behaviour was observed for
Ti6Al4V ELI, however, Ti6Al7Nb showed lower current
densities than Ti6Al4V ELI. With increase in immersion time,
a steady passive current was observed indicating a stable surface
film on Ti6Al7Nb alloy.
The enhanced passive film formation for the alloy Ti6Al-
7Nb can be attributed to the presence of Nb. The effects of Nb as
an alloying element in stabilizing the surface films on Ti based
alloys have been reported [5]. Also, the Nb cations improve the
passivation properties of surface film by decreasing the concen-
tration of anion vacancies present on titanium oxide film. These
anion vacancies are generated by the presence of lower titanium
oxidation states [9,10]. Hence, the low current density obtained
for Ti6Al7Nb compared to Ti6Al4V ELI might be due to
the effect of Nb in the passive film of the former. The better
corrosion performance of Ti6Al7Nb alloys in Hanks solution
has also been reported earlier by the same authors [11,12].
The stable current during prolonged immersion can be
attributed to a continuous interaction of calcium and phosphate
ions present in the SBF solution, with the surface film formed on
titanium alloys [13]. Hodgson et al. [14] reported the interaction
of ions present in the Hanks solution on the surface of titanium
alloy and the changes induced on the surface film properties.
3.2. Electrochemical impedance spectroscopic (EIS)
studies
3.2.1. Impedance results for the Ti6Al7Nb alloy in
simulated body uid solution
Impedance spectra for Ti6Al7Nb alloy at different immer-
sion hours (0, 120, 240 and 360 h) in SBF solution are repre-
841
Fig. 2. Impedance spectra of Ti6Al7Nb alloy at different immersion hours in
SBF solution: (a) Bode plot (log|Z| vs. log f) and (b) Bode plot (phase angle vs.
log f).
sented as Bode plots and are shown in Fig. 2a and b. Fig. 2a
showing the |Z| Bode plot, exhibited a high impedance value at
0 h of immersion, whereas the impedance values decreased with
increase in immersion time till 240 h. However, after 240 h there
was no significant change in impedance values.
From Fig. 2b, the phase angle observed at low frequency for
immediate immersion was nearly 40 . However, at interme-
diate frequency, the phase angle shifted to 90 and remained
constant over a wide range of frequency, indicating a near capac-
itive response for the alloy. However, with increase in time to
240 h of immersion the alloy exhibited two distinct capacitive
behaviours. Besides, at low frequency, the phase angle values
were shifted to 60 . At 360 h of immersion, the nature of Bode
plots was similar to that of 240 h of immersion. The fitted Bode
plots for Ti6Al7Nb at 0 and 360 h are seen in Fig. 3.
The high impedance values and phase angle of 90 are
indicative of a single thin passive oxide film present on the sur-
face at 0 h of immersion. The decrease in the impedance value
observed for 240 and 360 h of immersion indicated a decrease
in corrosion resistance of the film. The two distinct capacitive
842 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846

Fig. 3. Fitted bode impedance spectra of Ti6Al7Nb alloy immersed in SBF

solution for 0 and 360 h.

behaviours can be attributed to the formation of a new layer

in addition to the barrier layer. The unchanged bode plots at
240 and 360 h of immersion indicated no further changes with
increase in immersion time after 240 h. This behaviour may be
due to the complete surface coverage of the new layer over the
barrier layer. Substantial evidence from literature [1517] shows
that the film formed on surface, after prolonged immersion in
SBF solution exhibits a two-layer structure composed of a dense
inner layer and a porous outer layer.

3.2.2. Impedance results for the Ti6Al4V ELI alloy in

SBF solution
The Bode plots for the alloy Ti6Al4V ELI at different
immersion hours (0, 120, 240 and 360 h) in SBF solution are
shown in Fig. 4a and b. The |Z| Bode plot shown in Fig. 4a
revealed decrease in the impedance with increasing time showed
Fig. 4. Impedance spectra of Ti6Al4V ELI alloy at different immersion hours
concordant values after 240 h of immersion. Fig. 4b exhibits a in SBF solution: (a) Bode plot (log|Z| vs. log f) and (b) Bode plot (phase angle
nearly capacitive response illustrated by a phase angle close to vs. log f).
90 over a wide range of frequency, indicating a compact pas-
sive film. As the immersion hour increased (120 h), the phase
angle decreased to nearly 65 and there was difference in the
profiles at the high and medium frequency region, but there
existed a significant difference in the response at lower frequen-
cies. The fitted Bode plots for 0 and 360 h are shown in Fig. 5.
As in the case of alloy Ti6Al7Nb, similar behaviour was
observed for Ti6Al4V ELI alloy. However, the phase angle
observed for the Ti6Al4V ELI alloy with increase in immer-
sion time at lower frequency region was suppressed compared
to Ti6Al7Nb alloy. In addition, at high frequency region the
phase angle was enhanced in the case of Ti6Al4V ELI. It is
evident that the impedance values for Ti6Al4V ELI alloy was
less than Ti6Al7Nb alloy.
The changes in the resistance of the passive film of the mate-
rials can be attributed to structural changes in the film or changes
in the ionic or electrical conductivity of the film. In the case of
Ti6Al4V alloy, it has been reported that the vanadium oxide
formed on the surface of Ti6Al4V alloy dissolves and this
dissolution of vanadium oxide is further enhanced by presence Fig. 5. Fitted bode impedance spectra of Ti6Al4V ELI alloy immersed in
of Cl ions in Hanks solution [10]. Dissolution of vanadium SBF solution for 0 and 360 h.
 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846 843

Table 3
Values of fitting parameters obtained by fitting Rs (Q1 R1 ) and Rs (Q1 R1 )(Q2 R2 ) model to the EIS data as a function of different immersion hours in SBF solution for
Ti6Al7Nb alloy
Rs (R1 Q1 )

Rs ( cm2 ) Q1 (F cm2 ) n1 R1 (M cm2 )

0h 11.26 6.515 0.9984 1.434

Rs (R1 Q1 )(R2 Q2 )

Rs ( cm2 ) Q1 (F cm2 ) n1 R1 (K cm2 ) Q2 (F cm2 ) n2 R2 (K cm2 )

120 h 10.11 40.178 0.8998 0.8732 1.9628 0.8261 50.280

240 h 3.99 0.8680 0.7320 0.2954 27.9352 0.7908 38.298
360 h 3.81 0.8661 0.7324 0.2960 49.3571 0.7353 38.301

oxide results in the generation and diffusion of vacancies in the charge transfer resistance (R1 0.3 K cm2 ), due to the newly
oxide layer of Ti6Al4V alloy. The same phenomena can be formed layer that accounts for higher protection.
attributed to the change in passive behaviour of Ti6Al4V alloy Table 4 summarizes the impedance results of the Ti6Al4V
with immersion time in Hanks solution (contain Cl ions) in the ELI alloy. The obtained impedance results are depicted in the
present study. form of an equivalent circuit as shown in Fig. 6. The exponent
of the CPE, n1 in the case of Q1 equals a value in between 0.85
3.2.3. Equivalent circuit tted for titanium alloys and 0.70, while n2 equals a value in between 0.74 and 0.69 in
The impedance spectra were modeled by fitting these data the case of Q2 . This indicates that Q2 corresponds to a capaci-
with an equivalent circuit. The software {EQUIVCRT} designed tance of the inner layer while, Q1 is a consequence of frequency
by Boukamp was used in this study for EIS data modeling dispersion of the outer layer [20]. In case of Ti6Al4V ELI
[18,19]. The impedance spectra were fitted using a non-linear alloy, the charge transfer resistance of the outer layer changes
least square (NLLS) fitting procedure. The results of the anal- from Rout 0.73 to 0.27 K cm2 , while the value of parameter
ysis are shown in Table 3. Here, Q and n are the magnitude Q1 6.84.2 F cm2 representing the capacitance of the outer
and the exponent of the constant phase element (CPE), respec- layer with increase in immersion times, i.e., 240360 h. The
tively, described by an empirical impedance function of the type resistance of the outer layer increases and reaches almost a con-
[19]: stant value for 360 h for Ti6Al4V ELI alloys in the SBF solu-
tion. Ti6Al7Nb alloy shows better corrosion resistance and
ZCPE = [Q(jw)n ]1 stability than Ti6Al4V ELI alloy for 360 h in SBF solution.
Fig. 7a and b shows the error distribution (E%) for
where, the constant Q accounts for a combination of properties
Ti6Al7Nb and Ti6Al4V ELI alloy in SBF solution. A rea-
related to both the surface and the electroactive species, j is the
sonable fit to the equivalent circuit for a given impedance spectra
complex variable for sinusoidal perturbations with = 2f, and
n being the exponent of CPE, with values between 1 and 1.
Gonzalez and Mirza Rosca [2] proposed Rs (Q1 R1 ) as the
equivalent circuit model to fit the EIS data in case of a sin-
gle passive film present on the metal surface. Similarly, in the
equivalent circuit seen in Fig. 6a for 0 h of immersion in SBF,
consists of the following elements; a solution resistance (Rs ) of
the test electrolyte (Q1 ), the double layer capacitance and R1 ,
the charge transfer resistance of the barrier layer. The physical
model for this equivalent circuit, Rs (Q1 R1 ) has also been shown
in Fig. 6a. From Table 3, it can be seen that the values of n were
very close to one (n > 0.9) for Ti6Al7Nb alloy at 0 h of immer-
sion in SBF solution. This indicated a near ideal capacitance of
the passive films formed on the Ti alloys. As the immersion
hours increased from 120 to 360 h, the equivalent circuit fitted
for Ti6Al7Nb (Fig. 6b) was Rs (Q1 R1 )(Q2 R2 ), where Q1 rep-
resents the double layer capacitance of the outer layer and Q2
the double layer capacitance of the inner layer, R1 and R2 are the
charge transfer resistance of the outer layer and inner layer of the
metal/electrolyte interface, respectively. The Ti6Al7Nb alloy Fig. 6. Equivalent circuit fitted for Ti6Al7Nb and Ti6Al4V ELI alloys in
at 360 h of immersion in SBF solution showed higher values of SBF solution: (a) 0 h and (b) 360 h.
844 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846

Table 4
Values of fitting parameters obtained by fitting Rs (Q1 R1 ) and Rs (Q1 R1 )(Q2 R2 ) model to the EIS data as a function of different immersion hours in SBF solution for
Ti6Al4V ELI alloy
Rs (R1 Q1 )

Rs ( cm2 ) Q1 (F cm2 ) n1 R1 (M cm2 )

0h 11.452 5.7785 0.8944 1.1592

Rs (R1 Q1 )(R2 Q2 )

Rs ( cm2 ) Q1 (F cm2 ) n1 R1 (K cm2 ) Q2 (F cm2 ) n2 R2 (K cm2 )

120 h 9.66 6.8785 0.8511 0.7308 3.1807 0.7476 48.608

240 h 9.856 4.9464 0.7036 0.2746 4.5214 0.7187 29.428
360 h 9.782 4.2214 0.7040 0.2749 6.4678 0.6956 29.484

can be established by admitting a relative error of less than 1% nium oxide film in water from a thermodynamic point of view
for the real and imaginary parts of the impedance [18]. Next, can be represented by reaction:
the quality of fitting was judged by the error distribution versus
the frequency comparing experimental with simulated data for {TiO2 }solid + 2H2 O Ti(OH)4(aq) (1)
different models. The fitted circuit for the obtained impedance
data has an error distribution less than 1% and the circuit showed Since, the majority of the dissolved species has been found to
a perfect fitting for Ti6Al7Nb than Ti6Al4V ELI alloy in be uncharged [22].
SBF solution.

3.2.4. Mechanism for apatite layer formation

Titanium surface covered by a natural oxide film have been
studied in a variety of media such as ringer, saliva, phosphate-
buffered saline solution, or serum [21]. Dissolution of the tita-

Fig. 7. Fit errors of Zreal and Zimaginary of (a) Ti6Al7Nb and (b) Ti6Al4V Fig. 8. SEM micrographs of titanium alloys immersed in SBF solution for 360 h:
ELI alloys at 360 h immersion in SBF solution. (a) Ti6Al7Nb and (b) Ti6Al4V ELI alloys.
 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846
The presence of a very small amount of charged corrosion
products is expected to induce minimal unwanted biochemical
reactions such as strong protein binding and unfolding:
{TiO2 }solid + 2H2 O [Ti(OH)3 ]+ (aq) + OH
{TiO2 }solid + 2H2 O [TiO2 OH ](aq) + H3 O+
The calcium ions present in the SBF solution tends to attach to
the titanium oxide surface upon immersion. The concentrations
of calcium and phosphate ions at the surface and therefore the
thickness of the calcium phosphate were observed to increase
with the immersion time [23]:
{TiOH}solid + Ca2+ (aq) {TiO Ca2+ (aq) }solid + H+ (aq)
Fig. 9. EDAX analysis of titanium alloys immersed in SBF solution for 360 h:
(a) Ti6Al7Nb and (b) Ti6Al4V ELI alloys.
845
{TiOH}solid + H2 PO4 (aq)
{Ti H2 PO4(aq) }solid + OH (aq) (5)
(2) Eq. (4) shows that the influence of cations (Ca2+ , Mg2+ ) adsorp-
tion on the surface and Eq. (5) shows the exchange of basic
(3) hydroxide anions (OH ) with phosphate anions:
3Ca2+ (aq) + 2PO4 3 (aq) {Ca3 (PO4 )2solid } (6)
Sitting [24] studied the immersion studies in the HBSS elec-
trolyte using XPS on CpTi and Ti6Al7Nb samples. The alloys
Ti6Al4V and Ti6Al7Nb behaved rather similarly to CpTi,
although a slight tendency to slower kinetics for the calcium
phosphate deposition out of HBSS (Hanks balanced salt solu-
tion) and EBSS (Earles balanced salt solution), respectively,
(4)
was noted [21].
3.3. SEM and EDAX studies
Fig. 8 shows the SEM images of Ti6Al7Nb and Ti6Al4V
ELI alloys immersed in SBF solution for 360 h. After immersion,
apatite layer was formed on the surface of the alloy as shown in
Fig. 8a and b. The composition of the particles was analyzed by
EDAX method and the results are shown in Fig. 9a and b.
The EDAX results indicated that the titanium peak was sup-
pressed for apatite formed on the alloys. This can be attributed
to the prolonged interaction of Ca and P over the surface of
the alloys, which in turn, increases the thickness of the layer.
These results are in good agreement with the electrochemical
polarisation and impedance spectroscopic studies.
4. Conclusions
The electrochemical techniques used in this investigation led
to the following conclusions.
A very low current density was obtained for Ti6Al7Nb
alloy than Ti6Al4V ELI alloy at 360 h in SBF solution due to
the stable passive film formed on surface of Ti6Al7Nb alloy.
The EIS results indicated the presence of a single passive layer
immediately after immersion for both the alloys. However, the
alloy immersed for 360 h in SBF solution exhibited the presence
of a bi-layered surface corresponding to an inner layer and an
outer layer. Further, the films formed on the alloys were con-
firmed by SEM and EDAX analysis as calcium and phosphate
may be due to apatite formation.
References
[1] J. Pan, D. Thierry, C. Leygraf, Electrochim. Acta 41 (1996) 1143.
[2] J.E. Gonzalez, J.C. Mirza Rosca, J. Electroanal. Chem. 471 (1999) 109.
[3] F. Toumelin-chemia, F. Rouelle, G. Burdairon, J. Dent. 24 (1996) 109.
[4] M.F. Semlitsch, H. Weber, R.M. Streicher, R. Schon, Biomaterials 13
(1992) 781.
[5] E. Kobayshi, T.J. Wang, H. Doi, T. Yoneyama, H. Hamanaka, Mater. Sci.:
Mater. Med. 9 (1998) 567.
[6] D. Rogers, D.W. Howie, S.E. Graves, M.J. Pearcy, D.R. Haynes, J. Bone
Joint Surg. 79B (1997) 311.
[7] J. Pan, D. Thierry, C. Leygraf, J. Biomed. Mater. Res. 28 (1994) 113.
846 S. Tamilselvi et al. / Electrochimica Acta 52 (2006) 839846
[8] T.M. Silva, J.E. Rito, A.M.P. Simoes, M.G.S. Ferreira, M. Da Lunha Belo,
K.G. Watkins, Electrochim. Acta 43 (1998) 203.
[9] S.Y. Yu, J.R. Scully, Corrosion 53 (1997) 965.
[10] M. Metikos-Hukovic, A. Kwokal, J. Piljac, Biomaterials 24 (2003) 3765.
[11] S. Tamilselvi, N. Rajendran, Proceedings of International Conference on
Corrosion (CORCON), Chennai Trade Center Complex, Chennai, India,
November 2830, 2005.
[12] S. Tamilselvi, V. Raman, N. Rajendran, Proceeding of International Con-
vention on Surface Engineering (INCOSURF), ISRO Satellite Center,
Bangalore, India, August 2527, 2004.
[13] A. Choubey, R. Balasubramaniam, B. Basu, J. Alloys Compd. 381 (2004)
288.
[14] A.W.E. Hodgson, Y. Mueller, D. Forster, S. Virtanen, Electrochim. Acta
47 (2002) 1913.
[15] N.D. Tomashow, G.P. Chernova, Y.S. Ruscol, G.A. Ayuyan, Electrochim.
Acta 19 (1974) 159.
[16] M.M. Hefny, A.A. Mazhar, M.S. El-Basiouny, Br. Corros. J. 17 (1982) 38.
[17] M.S. El-Basiouny, A.A. Mazhar, Corrosion 38 (1992) 237.
[18] B.A. Boukamp, Equivalent Circuits, Manual AC Immittance Data
Analysis System, Ensehde: University of Twente, The Netherlands,
1989.
[19] B.A. Boukamp, Solid State Ionics 21 (1986) 31.
[20] E. Tkalcec, M. Sauer, R. Nonninger, H. Schmidt, J. Mater. Sci. 36 (2001)
5253.
[21] M. Textor, C. Sitting, V. Frauchiger, S. Tosatti, D.M. Brunette, Titanium
in Medicine: Material Science, Surface Science, Biological Responses and
Medical Applications, Springer-Verlag, Heidelberg, 2001, p. 171.
[22] S.G. Steinemann, Periodontology 17 (1998) 7.
[23] T. Hanawa, M. Ota, Biomaterials 12 (1991) 767.
[24] C.E. Sitting, Ph.D. Thesis Nr. 12657, Swiss Federal Institute of Technology
(ETH), Zurich, Switzerland.