Materials Chemistry and Physics 86 (2004) 269278

Investigation on the corrosion behavior of Ti6Al4V

implant alloy by electrochemical techniques
Robert Wen-Wei Hsu a , Chun-Chen Yang b, , Ching-An Huang c , Yi-Sui Chen b
a Department of Orthopedics, Chang Gung Memorial Hospital, Kwei-Shan 333, Taiwan, ROC
b Department of Chemical Engineering, Ming-Chi Institute of Technology, Taipei 243, Taiwan, ROC
c Department of Mechanical Engineering, Chang Gung University, Kwei-Shan 259, Taiwan, ROC

Received 26 December 2003; received in revised form 19 January 2004; accepted 3 February 2004

Abstract
The electrochemical corrosion behaviors of Ti6Al4V implant alloy were studied in three biological fluid solutions, i.e. urine, serum and
joint fluid. For comparison, the corrosion characteristics of Ti6Al4V implant alloys were also investigated in phosphate buffered saline
(PBS) solutions at different pH values and temperatures. The electrochemical corrosion properties of Ti6Al4V alloys were investigated
by electrochemical techniques, such as cyclic voltammetry, potentiodynamic method, and ac impedance spectroscopy. The corrosion
resistance of Ti6Al4V implant alloys in different biological solutions was evaluated in terms of corrosion potential (Ecorr ), corrosion
current density (icorr ) and polarization resistance (Rp ). The corrosion kinetic parameters were calculated from both the Tafel extrapolation
analysis and ac impedance analysis. It was observed that the corrosion current densities of Ti6Al4V implant alloy in PBS solutions of
different pH values were about the same order of magnitude, which was at a level of 12 A cm2 at 37 C. In contrast, the corrosion
current densities in biological fluids were lower at an order of 0.10.3 A cm2 at 37 C. The ac circuit elements for corrosion interface
of Ti6Al4V alloy in various solutions were reported based on the Randle equivalent circuit model. It was found that the Ti6Al4V
implant alloy in three biological body fluid solutions showed a characteristic of one capacitive behavior. The experimental results obtained
from different electrochemical techniques were compared and discussed.
2004 Elsevier B.V. All rights reserved.
Keywords: Ti6Al4V alloy; Corrosion; ac impedance; Biological fluids; Tafel plot

1. Introduction ments [3045] and hydroxyapatite (HA) coating [10,31] on

Implant alloys exhibit attractive properties such as me-
chanical strength and biocompatibility [1,2], corrosion
resistance [329], safety, ductility, and wear resistance
[3045]. It was rarely found the study on corrosion behavior
of Ti6Al4V implant alloy in human body fluid in the lit-
erature. Many studies have shown that the electrochemical
corrosion is one of failure modes of Ti-based implant alloy
materials [4651]. It might have some relationships with
the late loosening of the implanted prosthetic components,
the long-term impact on the alteration of metabolism, im-
munity and the potential incidence of malignant tumor. The
failure of Ti-based metal alloy prosthetic component may be
caused by the interaction of electrochemical corrosion and
wear mechanism in the biological corrosion environment.
Some authors have investigated the effect of surface treat-
Corresponding author. Tel.: +886-2-2908-4309;
fax: +886-2-2904-1914.
E-mail address: ccyang@ccsun.mit.edu.tw (C.-C. Yang).
the metal alloys to reduce the corrosion of implant alloy
materials.
The compositions of Ti6Al4V implant alloys (Johnson
Matthey Co.) are with the major elements of 87.73 wt.% of
Ti, 6.85 wt.% of Al and 5.42 wt.% of V. The Ti6Al4V im-
plant alloys were used on the tibial component for total knee
arthroplastry (TKA) prosthesis. Although, the Ti6Al4V
implant alloy has an excellent corrosion resistance, it was
found the titanium, aluminum and vanadium were released
into the cell tissue by the way of the passive film dissolu-
tion [32] and wear corrosion process [6,30,46]. Vanadium
is classified in the toxic group [6]. Basically, the stronger
and stable the TiO2 passive film on the Ti-based implant al-
loy, the better the corrosion resistance and also less the re-
lease of the metal ions from the alloys. It was believed that
the implanted alloy was corroded in biological body fluids
due to the loosening of prosthesis, infection, wear or fret-
ting corrosion, and metabolism [3,50]. Experimental results
found that the released metallic ion concentrations from the
impaired Ti6Al4V alloy in joint fluid were significantly

0254-0584/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2004.02.025
270 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278
higher than that of serum as well as urine after analyses of
the impaired implant alloy [47].
This work is to study the electrochemical corrosion char-
acteristics of Ti6Al4V implant alloy in PBS solutions as
well as in body fluid solutions. In order to understand the
failure mechanism of Ti6Al4V implant alloy in the bio-
logical environment, the corrosion behavior of implant alloy
was examined by the cyclic voltammetry, the potentiody-
namic and ac electrochemical impedance measurements.
2. Experimental
Commercial Ti6Al4V implant alloys (Johnson Matthey
Co.) were used in this work. The plate samples were cut
with an exposed area of 1 cm2 . A Ni wire was soldered on
the rear side of sample and the test sample was then embed-
ded in an epoxy resin. The test sample surface was abraded
using 600, 800 and 1000 grit emery papers and then pol-
ished with 0.1 m Al2 O3 paste. Before the electrochemical
measurement, the specimens were cleaned in alcohol us-
ing ultrasonic bath for 10 min, then degreased with acetone,
washed with doubly distillated water and then transferred to
the electrochemical cell. The specimens were mounted by
epoxy resin in such that only the flat surface contacted with
the electrolytes.
A phosphate buffered saline (PBS) solution (Merck) was
used as an electrolyte for all electrochemical measurements.
The PBS solution contains similar ion concentrations as
blood. The chemical composition of this solution is 0.17 M
Na+ , 0.02 M K+ , 0.05 M H+ , 0.15 M Cl and 0.03 M
PO4 3 . The PBS solution is commonly used for in vitro
corrosion studies of implant alloy biomaterial [8,46]. The
pH value of PBS electrolyte solution was varied between
four and nine. The temperature of the measurement system
was varied between 25 and 45 C. The desired temperatures
for electrochemical tests were maintained throughout tests
by using a water bath. The PBS solution of pH value of four
or nine could be adjusted by adding 1N HCl or 1N NaOH
solution. The three biological body fluids, i.e. serum, joint
fluid and urine, were collected and prepared from Chang
Gung Memorial Hospital (Taipei, Taiwan). In addition, the
pH values of biological fluid solutions were measured be-
fore test. The pH of serum was at a range of 7.67.7, a
pH range of 6.16.6 for urine and a pH range of 7.98.2
for joint fluid. All the test electrolytes were no de-aerated
condition. Three specimens were carried out for each test
conditions. All specimens were tested at least three times.
The experimental setup for the polarization curves mea-
surement consisted of a three-electrode electrochemical
glass cell. The volume of cell was 100 ml. The implant
alloy specimens were used as a working electrode, a large
area of Pt screen used as a counter-electrode and a satu-
rated calomel electrode (SCE) as a reference. The mea-
surements for the polarization curves were recorded at a
corrosion potential (Ecorr ) 250 mV range with a scan rate
of 0.5 mV s1 . The steady-state cyclic polarization curves
were obtained in the potential range 150 to +1000 to
2500 mV versus Ecorr with the scan rate 0.5 mV s1 . The
polarization measurement experiments were carried out at
least three times. An EG&G 273A potentiostat (Princeton
Applied Research) with a corrosion software Zplot2 and
Zview2 (Scribner Association Inc.) was used for electro-
chemical control and data analyses. The corrosion current
density (icorr ) and kinetics parameters (anodic and cathodic
Tafel slopes, ba and bc ) were obtained from the Tafel
analysis of polarization curves.
The ac impedance spectra for Ti6Al4V implant alloys
in PBS solutions as well as in body fluids were obtained
by using EG&G 273A system connected with a PAR 5210
lock-in amplifier (Princeton Applied Research). The scan
frequency range was set at 300 kHz to 10 mHz with the
perturbation amplitude of 10 mV. The polarization resistance
(Rp ) from ac spectra analysis was obtained by using the
Zview2 software.
3. Results and discussion
3.1. Polarization behavior
Fig. 1 shows the polarization curve for Ti6Al4V im-
plant alloy in PBS solutions of different pH values at 37 C.
A cathodic Tafel slope of approximately 5070 mV per
decade was observed, which indicated the oxygen reduction
takes places at the metal surface. Fig. 2 displays the polar-
ization curve for Ti6Al4V implant alloy in different bio-
logical fluids at 37 C. The mean corrosion potential (Ecorr ),
mean corrosion current densities (icorr ), anodic and cathodic
Tafel slopes (ba and bc ) for Ti6Al4V implant alloy in
different solutions at 37 C is listed in Table 1. Moreover, it
was experimentally observed that the corrosion current den-
sity (icorr ) for Ti6Al4V implant alloy in de-ionized (DI)
water at 37 C was about 0.06 A cm2 . It was reported that
the corrosion current density of Ti4Al4V implant alloy is
as high as 45.93 A cm2 in 0.6 M NaCl solution at room
temperature [18], 38.48 A cm2 in 15 wt.% H2 SO4 solu-
tion, 13.35 A cm2 in 7.5 wt.% HCl solution [19]. In this
study, it was observed that the corrosion current densities of
Ti6Al4V in PBS solution at 37 C were slightly affected
at a range of 1.253.42 A cm2 when the pH value varied
at a range of 49.
3.2. Cyclic voltammetry analysis
Fig. 3 presents the cyclic voltammogram for Ti6Al4
implant alloy in PBS solutions at different pH values at 37 C
with the scan rate of 0.5 mV s1 . A small range of passive
region for Ti6Al4V implant alloy was observed in the
potential range of 0.25 to +0.25 V (versus SCE) in PBS
solutions of pH 7 and 9. No passive region for Ti6Al4V
implant alloy was observed in the potential range of 0.25
 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278 271

-0.15
pH 4
-0.20
pH 7
-0.25 pH 9
Deionized (D.I.) water
-0.30

-0.35

-0.40
E (vs. SCE)/ V

-0.45

-0.50

-0.55

-0.60

-0.65

-0.70

-0.75

-0.80
-7.0 -6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0
-2
log ( i )/ (Acm )

Fig. 1. Tafel plot for Ti6Al4V alloy in PBS solutions at different pH values.

-0.25 Joint fluid

Serum
Urine
-0.30

-0.35
E (vs. SCE) / V

-0.40

-0.45

-0.50

-0.55

-0.60
-7.5 -7.0 -6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0
-2
log ( i ) / (A cm )

Fig. 2. Tafel plot of Ti6Al4V implant alloy in various biological fluids at 37 C.

Table 1
Electrochemical kinetics parameters for Ti6Al4V alloys in various simulated PBS and biological fluid solutions at 37 C
Electrolyte Parameters
ba (mV per decade) bc (mV per decade) icorr (A cm2 ) Ecorr (V)
PBS at pH 4 50 9.2 70 8.02 3.42 1.02 0.320 0.20
PBS at pH 7 70 5.8 50 4.8 1.88 0.02 0.450 0.04
PBS at pH 9 75 7.2 61 4.1 1.25 0.14 0.430 0.06
Joint fluid 60 9.1 90 3.8 0.33 0.21 0.468 0.02
Serum 88 10.8 40 2.8 0.15 0.22 0.442 0.05
Urine 121 11.8 80 6.8 0.11 0.14 0.398 0.18
272 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278

2.5 1.0
0.8
2.0
0.6
E (vs.SCE) / V

1.5
E (vs. SCE) / V

0.4

1.0 0.2
0.0
0.5 Ecorr,f
-0.2 Ecorr,f
0.0 Ecorr,s -0.4 Ecorr,s

-0.5 -0.6

-1.0 -8 -7 -6 -5 -4 -3 -2 -1
-2
-8 -7 -6 -5 -4 -3 -2 -1 0 (a) log ( i )/(Acm )
-2
(a) log ( i )/ (A cm )
1.0
0.8
0.6
E (vs.SCE) / V

0.4
E (vs. SCE) / V

0.2
0.0
E corr,f
-0.2
-0.4 E corr,s
E corr,f
E corr,s -0.6

-8 -7 -6 -5 -4 -3 -2 -1
-2
(b) log ( i )/(Acm )
-8 -7 -6 -5 -4 -3 -2 -1 0
(b)
-2
log ( i )/ (Acm ) 1.0
0.8
0.6
E (vs. SCE) / V

0.4
E (vs. SCE) / V

0.2
0.0 E corr,f
-0.2
E corr,s
-0.4
Ecorr,f -0.6
Ecorr,s

-8 -7 -6 -5 -4 -3 -2 -1
-2
(c) log ( i )/(A cm )
-8 -7 -6 -5 -4 -3 -2 -1 0
-2
(c) log ( i )/ (A cm ) Fig. 4. Cyclic voltamogram of Ti6Al4V implant alloy in three biological
fluids: (a) joint fluid; (b) serum; (c) urine at 37 C.
Fig. 3. Cyclic voltammogram of Ti6Al4V implant alloy in PBS solution
of different pH values at 37 C: (a) pH 4; (b) pH 7; (c) pH 9.

vations would be in favor of the adsorption mechanism of

to +2.50 V (versus SCE) in PBS solution of pH 4. The
anodic current density of Ti6Al4V alloy increased steeply
at a potential higher than 0.25 V, indicating the oxide passive
layer broke down, starting forming pits.
In contrast, it was found that there is no apparent passive
region for Ti6Al4V implant alloy in PBS solution of pH
4 in acidic solution. Following passivity breakdown and re-
versing the potential direction, a pronounced hysteresis was
observed, a typical of adsorption mechanism of passivity
breakdown process and a pit initiation occurred. The obser-
passivity breakdown and pit initiation, which assumes that
the chloride forms complex at the surface of oxide passive
film. The aggressive chloride ions will enhance the corro-
sion of metallic implant alloys.
Fig. 4 shows the cyclic voltammogram for Ti6Al4V im-
plant alloy in three biological fluids at 37 C. It was found
that the alloy remains in passive state within a narrow po-
tential range before the pitting potential (Epit ) or breakdown
potential (Eb ) was reached. The Epit is a useful parameter in
assessing pitting properties of metal materials. The Epit can
 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278 273

Table 2 of Ti6Al4V in electrolyte solution [6,30]. However, no

The values of Epit and Ep for Ti6Al4V implant alloy in various bi- passive region of Ti6Al4V implant alloy in serum, the
ological solutions at 37 C with a scan rate of 0.5 mV s1 for cyclic
value of Ep could not be estimated. The corrosion resistance
voltammetry analysis
of Ti6Al4V implant alloy in serum solution environment
Electrolyte Parameters cannot be directly compared by the value of Epit Ep .
Ecorr,s Ecorr,f Epit (V) Ep (V) Epit = Alternatively, the narrower hysteresis loop in cyclic
(V) (V) Epit Ep (V) voltammogram, the more corrosion resistance for Ti6Al4V
PBS at pH 4 0.148 0.305 0.450 implant alloys in body fluids. It was found that the values
PBS at pH 7 0.471 0.240 0.250 0.200 0.450 of Epit Ep for Ti6Al4V alloy in PBS solutions at pH 7
PBS at pH 9 0.411 0.261 0.250 0.230 0.480
and 9 are much higher than that of in biological body fluids.
Joint fluid 0.456 0.305 0.180 0.220 0.04 It was seen that Ti6Al4V implant alloy in PBS solution
Serum 0.458 0.234 0.100 was less corrosion resistant than that of Ti6Al4V alloy
Urine 0.442 0.120 0.250 0.070 0.320
in biological body fluid. In addition, the more noble Ecorr,f
Ecorr,s is the starting corrosion potential; Ecorr,f is the final corrosion (Ecorr,f is the Ecorr in the reverse scan) in cyclic voltammo-
potential. gram, the more corrosion resistant for Ti6Al4V implant
alloys in biological fluids. It was found that the value of
be defined as the potential where a continuous increase in Ecorr,f for Ti6Al4V alloy in joint fluid solution was much
the anodic current in the dynamic polarization analysis. The less noble than that of in serum and in urine, as shown
values of the pitting potential (Epit ) and the pitting protec- in Table 2. The mean passivity current density (ipass ) for
tion potential (Ep ) for Ti6Al4V implant alloy at 37 C in Ti6Al4V alloy in three biological fluids were examined
various solutions at different pH values are listed in Table 2. from Fig. 4. Furthermore, it was found that the Ti6Al4V
It was believed that the pitting corrosion process of metals implant alloy in joint fluid (ipass = 12.6 A cm2 ) was less
in chloride-containing solution involves four steps [16,17]: corrosion resistant than that of Ti6Al4V alloy in urine
(1) formation of the passive layer, (ii) breakdown of pas- (ipass = 3.16 A cm2 ) solution, as indicated in Fig. 4.
sive layer, (iii) growth of unstable pits or metastable pits
which can be repassivated and (iv) growth of larger and sta- 3.3. ac impedance analysis
ble pits. Furthermore, pits have been shown to further de-
velop into other forms of localized corrosion [30]. While Fig. 5 presents the Nyquist plot (experimental data and
the difference in the values of Epit as well as different hys- theoretical Randle model prediction lines) for Ti6Al4V
teresis behaviors of Ti6Al4V implant alloy in body flu- implant alloy in PBS solutions of different pH values at
ids could be due to the pitting mechanism. The smaller the Ecorr at 37 C. Theoretical model predictions are in good
value of Epit Ep , the higher is the corrosion resistance agreement with the experimental results. Fig. 6 shows the

-1600
pH 7 (exp.)
-1400 pH 4 (exp.)
pH 9 (exp.)
pH 7 (model)
-1200 pH 4 (model)
pH 9 (model)

-1000
Z"/ (ohm cm )
2

-800

-600

-400

-200

0
0 500 1000 1500 2000 2500 3000 3500 4000
2
Z' / (ohm cm )

Fig. 5. Nyquist impedance spectra of Ti6Al4V implant alloy in PBS solutions of different pH values at Ecorr at 37 C: symbol: experimental data; line:
model prediction.
274 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278

-20000

-18000

-16000

-14000
Z"/ (ohm cm2)

-12000

-10000

-8000
joint fluid (exp.)
-6000 serum (exp.)
urine (exp.)
-4000 joint fluid(model)
serum (model)
urine (model)
-2000

0
0 3000 6000 9000 12000 15000 18000 21000 24000 27000
Z'/ (ohm cm2)

Fig. 6. Nyquist plot of Ti6Al4V implant alloy in biological fluid solutions at Ecorr at 37 C: symbol: experimental data; line: model data.

Nyquist plot for Ti6Al4V implant alloy in three different The value of Rs in PBS solutions of different pH values
biological fluids at Ecorr at 37 C. It was observed that the at 37 C is about the same order of 23  cm2 . The value
value of polarization resistance (Rp ) for Ti6Al4V implant of polarization resistance in PBS solution of pH 7 (Rp =
alloy in PBS solution of pH 4 was much less than that for 1311  cm2 ) is higher than that in PBS solution of pH 4
Ti6Al4V implant alloy in PBS solution of pH 7 and 9 at (Rp = 511  cm2 ). However, the value of polarization resis-
37 C. tance in neutral PBS solution (Rp = 1311  cm2 ) is lower
The impedance spectra for Ti6Al4V implant alloys in than that in PBS solution of pH 9 (Rp = 3426  cm2 ). Fur-
PBS and biological fluids are comprised of a single de- thermore, the element value of solution resistance (Rs ) in
pressed semicircle loop. This is indicated that the equiva- three biological fluids at 37 C is about the same order at
lent circuit of interface on the Ti6Al4V alloy is consisted a range of 36  cm2 . The value of polarization resistance
of the resistance of the electrolyte (Rs ), in series with the (Rp = 10 787 cm2 ) in joint fluid at 37 C is lower than
constant phase element (CPE) in parallel with the polariza- that in serum (Rp = 61 392  cm2 ) and in urine (Rp =
tion resistance (Rp ), a simple Randle equivalent circuit. The 246 830  cm2 ).
impedance of CPE is defined by The ac analysis results indicated that the corrosion of
1 Ti6Al4V implant alloys was all under charge-transfer con-
ZCPE = trol in PBS and in body fluid solutions at 37 C; however,
(j)n Q
showed different extent of corrosion resistance (with differ-
where j = 1, = 2f and the exponent n of the CPE is ent values of Rp ). The may be due to the lower pH value of
related to a non-equilibrium current distribution due to the PBS solution with aggressive ions Cl ions easily attack the
surface roughness. The parameter Q is a constant represent-
ing true capacitance of the oxide barrier layer. Instead of Table 3
ideal double layer capacitance, the CPE (which represents ac Impedance parameters for Ti6Al4V implant alloy in various solutions
the true capacitance) were used here. The impedance of CPE at Ecorr at 37 C
with the value of n is related to a non-uniform current dis- Electrolyte Parameters
tribution due to oxide layer surface roughness (porous) or
Rs ( cm2 ) Q (F cm2 ) n Rp ( cm2 )
non-homogeneity [25]. For interface behavior is an ideal ca-
pacitor having n = 1 and a maximum phase angle equal to PBS at pH 4 1.95 37 0.79 511
90 . The chi-square value (2 ) between 103 and 105 PBS at pH 7 1.86 79 0.66 1311
PBS at pH 9 2.24 36 0.63 3426
indicates excellent agreement between the experimental and
theoretical values, by using the CPE in the fitting procedure. Joint fluid 3.05 12 0.82 10787
All values of circuit elements for Ti6Al4V implant alloy Serum 5.98 14 0.86 61392
Urine 5.78 16 0.82 246830
in various solutions at Ecorr at 37 C are listed in Table 3.
 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278 275

5.0

4.5 Joint fluid (exp.)

Serum (exp.)
Urine (exp.)
4.0 Joint fluid (model)
Serum (model)
3.5 Urine (model)
log IZI / (ohm cm )
2

3.0

2.5

2.0

1.5

1.0

0.5
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
(a) log ( f ) / Hz

-100

joint fluid (exp.)

-90
serum (exp.)
urine (exp.)
-80
max=-74.4o joint fluid (model)
max=-72o serum (model)
-70 urine (model)

max= -60.7o
-60
/ deg.

-50

-40

-30

-20

-10

0
-2 -1 0 1 2 3 4
(b) log ( f )/ Hz

Fig. 7. Bode plot of Ti6Al4V implant alloy in three biological fluid solutions at Ecorr at 37 C.

TiO2 oxide passive layer [16], therefore reduce the corro-
sion resistance of Ti6Al4V implant alloy in PBS solution
of a pH 4. The compositions of protein ions and amino acids
or Cl ions in biological fluids for the corrosion behavior
of Ti6Al4V implant alloy have pronounced effect due to
local variation of pH [16].
Fig. 7a presents the Bode plot (log |impedance| versus
log |frequency|) for Ti6Al4V implant alloy in three bio-
logical body fluids at Ecorr at 37 C. It was observed that the
slope of impedance diagram in the middle frequency was
at a range of 0.69 to 0.82. Fig. 7b shows the Bode plot
(phase angle () versus log |frequency|) for Ti6Al4V im-
plant alloy in three biological fluids at Ecorr at 37 C. The
maximum phase angle ( max ) in three body fluids was mea-
sured at approximately from 64 to 74 . The maximum
phase angle was found less than 90 at intermediate fre-
quencies. It may be concluded that Ti6Al4V implant al-
loy interface behavior, due to formation of porous passive
oxide layer, having CPE with n < 1 and with a maximum
phase angle at a range of 63 to 74 . It may be due to the
roughness of oxide layer, attacking by aggressive Cl ions
or adsorption of protein ions from the solution medium [25].
It is apparently that the corrosion interface of Ti6Al4V
implant alloy in biological body fluids is a characteristic of
a capacitive behavior with only one time constant, as seen
in Fig. 7.
276 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278

-0.25

-0.30 25 oC
37 oC
45 oC
-0.35

-0.40
E (vs. SCE) / V

-0.45

-0.50

-0.55

-0.60

-0.65

-0.70
-7.0 -6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0
log ( i ) / (A c m-2)

Fig. 8. Tafel plot for Ti6Al4V implant alloy in PBS solution at pH 7 at different temperatures.

3.4. Temperature effect
Fig. 8 shows the polarization curve for Ti6Al4V im-
plant alloy in PBS solution of a pH 7 at different tempera-
tures. As seen in Fig. 8, the corrosion potential of Ti6Al4V
alloy was only slightly shifted to the noble direction (from
0.550 to 0.450 V) when the temperature of electrolyte in-
creased. Fig. 9 shows the Tafel plot for Ti6Al4V implant
alloy in joint fluids at different temperatures. It was observed
that the corrosion potential of Ti6Al4V implant alloy was
varied in a range of 0.5 to 0.4 V (versus SCE) when the
temperature increased. The mean values of corrosion cur-
rent densities for Ti6Al4V implant alloy in body fluid so-
lutions by Tafel slopes (by anodic and cathodic slopes at a
range of Ecorr 250 mV) extrapolation at different temper-
atures are listed in Table 4. Experimental results indicated
that the corrosion current densities were increased when the
temperature of body fluid solutions was increased.
It was found that the mean corrosion current densities of
Ti6Al4V implant alloy in PBS solutions were at a range of

o
-0.1 25 C
o
37 C
o
45 C
-0.2

-0.3
E (vs. SCE) / V

-0.4

-0.5

-0.6

-0.7

-0.8
-8.0 -7.5 -7.0 -6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0
log ( i ) / (A cm-2)

Fig. 9. Tafel plot of Ti6Al4V implant alloy in joint fluid solution at different temperatures.
 R.W.-W. Hsu et al. / Materials Chemistry and Physics 86 (2004) 269278
Table 4
The mean values of corrosion current densities (A cm2 ) for Ti6Al4V
implant alloy in various biological solutions at different temperatures
Electrolyte Corrosion current density
25 C 37 C 45 C
PBS at pH 4 2.89 0.15 3.42 0.25 10.9 2.15
PBS at pH 7 1.50 0.25 1.88 0.21 5.22 1.15
PBS at pH 9 1.01 0.07 1.25 0.18 1.95 1.11
Joint fluid 0.23 0.15 0.33 0.11 1.20 0.05
Serum 0.11 0.06 0.15 0.06 0.52 0.08
Urine 0.10 0.04 0.11 0.07 0.36 0.10
1.012.89 A cm2 at 25 C, a range of 1.253.42 A cm2
at 37 C and a range of 1.9510.9 A cm2 at 45 C. In con-
trast, the mean corrosion current densities in serum and urine
fluids were all less than 2 A cm2 at between 25 and 45 C.
Experimental results indicated that the increased tempera-
ture of electrolyte solution (three biological fluids) did not
significantly reduce the corrosion resistance of Ti6Al4V
alloy.
The ac impedance spectra for Ti6Al4V implant alloy
in joint fluids at Ecorr at different temperatures were also
measured. The value of polarization resistance (Rp ) in joint
fluid at different temperatures is at a range of 1 104 to
3 104  cm2 .
4. Conclusions
This work is to investigate the electrochemical corro-
sion behavior of Ti6Al4V implant alloy in various bi-
ological fluids by electrochemical techniques, such as the
cyclic voltammetry, the potentiodynamic method, and ac
impedance spectroscopy. It was experimentally found that
the Ti6Al4V implant alloys were significantly corroded
in PBS solution of pH 4 or at a higher temperature. The
corrosion resistance of Ti6Al4V alloys in joint fluid were
lower than that in serum and in urine. The corrosion resis-
tance characteristics of Ti6Al4V implant alloy were ex-
perimentally measured in terms of the corrosion potential,
the corrosion current density and ac polarization resistance.
The ac circuit elements for corrosion interface of Ti6Al4V
alloy in various fluid solutions were calculated based on the
simple Randle equivalent circuit model. Theoretical model
predictions are in good agreement with the experimental re-
sults. Experimental results for the Ti6Al4V implant alloy
in various fluid solutions obtained from the Tafel analyses as
well as ac impedance spectroscopy analyses were consistent.
Acknowledgements
The financial support for this study from the National
Science Council of the Republic of China under the Project
No. NSC-89-2314-B-82A-187 is gratefully acknowledged.
277
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