Trends Biomater. Artif. Organs, Vol 18 (2), January 2005 http://www.sbaoi.

org

Electrochemical Behavior of Ti-Based Alloys in Simulated Human

Body Fluid Environment
Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*
1
Sahajanand Medical Technologies, Surat 395003, India
*Department of Materials and Metallurgical Engineering
Indian Institute of Technology, Kanpur 208016, India
E-mail: animesh.med@sahmed.com

Abstract:
The electrochemical behavior of Ti and Ti-based alloys (in weight %) Ti-15Al, Ti-5Al-2.5Fe, Ti-6Al-
4V, Ti-6Al-4Fe, Ti-6Al-4Nb, Ti-13.4Al-29Nb and Ti-13Nb-13Zr have been studied in simulated human
body environment. Hanks solution was utilized for simulating body fluid conditions. Potentiodynamic
polarization experiments conducted at 37C indicated stable passive polarization behavior for all the
alloys. The electrochemical behavior of 316L stainless steel was also studied for comparison purposes.
Corrosion rates were determined by the Tafel extrapolation method. The corrosion rates of the Ti-alloys
were comparable but lower than that of 316L stainless steel. The Ti-alloys exhibited noble breakdown
potentials and large passive ranges compared to 316L stainless steel. Alloying Al to Ti in significant
amount lowered the passive range. Substitution of vanadium in Ti-6Al-4V with iron and niobium did
not significantly affect the electrochemical behavior. The passive current densities for the Ti alloys were
comparable and similar to that of 316L stainless steel. Microstructures of the surfaces used for
electrochemical testing have been discussed.

Keywords: Titanium, corrosion, simulated body fluid, electrochemical behavior, passivation.

Introduction: characteristics including low corrosion rate,

biocompatibility, strength, low modulus and
Corrosion of human body metallic implants is
density and the capacity for joining with bone
critical because it can adversely affect
and other tissues (osseointegration)(3).
biocompatibility and mechanical integrity (1).
Investigation of 316L stainless steel and Ti-
Corrosion and surface film dissolution are two
6Al-4V in deaerated simulated body fluid
mechanisms responsible for introducing
Hanks solution at 37C have revealed a high
additional ions in the body from the implants.
breakdown potential for Ti-6Al-4V (1900 mV
Extensive release of metal ions from human
vs. SCE) compared to 316L stainless steel (280
body implants can result in adverse biological
mV vs. SCE) (4). Ogundele and White carried
reactions and even lead to mechanical failure
out a series of polarization studies on surgical
of the device (2). The natural selection of
grade stainless steel in Hanks physiological
titanium alloys for human body implants is
solution under varying conditions of
determined by a combination of most favorable

64
 Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
temperature, chloride content and pH and they
reported that increasing concentrations of
chloride ions adversely affected corrosion
resistance in lowering breakdown potentials,
marginally lowering corrosion potentials,
lowering passivation potentials and generally
increasing the propensity to pitting attack as
evidenced by the increase in size of hysteresis
loops from potentiodynamic cycling tests (5).
Titanium scores well above 316L steel as the
passive film formed on titanium and its alloys
can resist attack due to chloride ions (6 - 8).
The physico-chemical and electrochemical
properties of the passive film and its long-term
stability in biological environments play a
decisive role in the biocompatibility of
titanium implants (9).
The effect of replacing vanadium in Ti-6Al-
4V by iron and niobium additions has been
evaluated in this study because of recent
reports that release of vanadium ions by the
way of passive dissolution or another process
involving wear can cause discoloration of the
surrounding tissue or an inflammatory reaction
causing pain and even leading to loosening
owing to osteolysis (10). The Ti-13Nb-13Zr
alloy has shown promising mechanical
properties (especially the elastic modulus
matching with that of bone) for implant
applications and therefore, this alloy was also
evaluated (11). Two Ti-based alloys developed
for use in aircraft engine components (Ti-15Al
and Ti-13.4Al-29Nb) were also studied. The
aim of the communication was to evaluate the
electrochemical behavior of these Ti-alloys in
simulated human body fluid condition and to
compare with that of 316L steel.
Experimental:
The materials used in the present investigation
were commercial purity (CP) Titanium, Ti-
15Al, Ti-5Al-2.5Fe, Ti-6Al-4V, Ti-6Al-4Fe,
65
Ti-6Al-4Nb, Ti-13.4Al-29Nb, Ti-13Nb-13Zr
and 316L steel (all compositions are in weight
%). All the alloys, except Ti-6Al-4V, 316L and
CP Titanium were received in form of pancakes
of dimension 6 cm diameter and 1 cm
thickness. They were procured from Defence
Metallurgical Research Laboratory,
Hyderabad, India. The Ti-6Al-4V, CP titanium
and 316L alloys were obtained in sheet form.
Dimensions of CP titanium sheet were 20 cm
20 cm and thickness 1cm. The 316L sheet
was of dimension 20 cm 20 cm and 0.5 cm
thickness. The dimension of Ti-6Al-4V was
10 cm 10 cm and 1 cm thickness. Specimens
for electrochemical studies were sectioned
from cast pancakes and sheets using a diamond
cutter (Buehler-ISOMET). In case of the
pancakes, the samples for electrochemical
testing were obtained from the top region of
the pancake. In case of CP Ti, Ti-6Al-4V and
316L, the rolling plane was mounted. The areas
to be exposed for electrochemical studies were
1 cm x 1 cm square. After soldering a wire to
the back of the specimen, each specimen was
cold mounted. Prior to the start of each
experiment, the cold mounted specimen was
polished up to 4/0 finish on emery paper and
then wet polished using 0.5 alumina powder.
The specimens were than washed in distilled
water followed by ultrasonic cleaning in
acetone. The electrochemical studies were
conducted using a Perkin Elmer 263A
potentiostat, interfaced to a computer. The
electrolyte used for simulating human body
fluid conditions was Hanks solution, prepared
using laboratory grade chemicals and double
distilled water. The pH of the solution was
precisely maintained at 7.4. Freshly prepared
solution was used for each experiment. The
composition of the Hanks solution used was
(in gm/l) 8 NaCl, 0.4 KCl, 0.14 CaCl2, 0.06
MgSO 4.7H 2O, 0.06 NaH 2PO 4.2H 2O, 0.35
 Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*

NaHCO3, 1.00 Glucose, 0.60 KH2PO4 and of free corrosion potential for Ti-13Nb-13Zr
0.10 MgCl2.6H2O. was different in some experiments compared
to other alloys. In this case the free corrosion
Electrochemical polarization studies were
potential shifted towards the active direction
conducted in a round bottom polarization cell.
before stabilization. The reason for the
The potential of the working electrode was
observed variation may be related to the nature
measured against saturated calomel electrode
of surface film that forms on the surface of Ti-
(SCE). The luggin capillary was placed close
13Nb-13Zr. Potentiodynamic polarization
to the working electrode. All the potentials
curves for the different Ti-based alloys are
mentioned in this paper are with reference to
shown in Fig 1 and 2. All the polarization and
SCE. A constant electrolyte temperature of
Tafel plots presented in this communication
372C was maintained using a heating
are conservative data (i.e. higher passive
mantle. All the potentiodynamic polarization
current density and higher corrosion rate)
studies were conducted after stabilization of
based on duplicate testing.
the free corrosion potential. The scan rate used
was 0.166 mV/s. The corrosion rate was
determined using the Tafel extrapolation
method, as per ASTM standard (12). All the
tests were duplicated. In some cases, additional
experiments were performed, especially if the
duplicate result was markedly different from
the original result.
The microstructures of the surfaces exposed
for electrochemical testing were also studied
using an optical microscope (Axiolab A, Zeiss, Fig 1: Potentiodynamic polarization curves for
Germany). The images were later analyzed in CP Titanium, Ti-5Al-2.5Fe, Ti-6Al-4V, Ti-6Al-4Fe,
an image analysis program (Image-Pro Plus, Ti-6Al-4Nb and 316L in Hanks solution at
version 4.1, Media Cybernetics, USA). The pH 7.4 and 37 C temperature.
microstructures were revealed by etching in
10% HF+5% HNO 3 solution for 5 to 10
seconds at room temperature. For the Ti-6Al-
4V, Ti-13.4Al-29Nb and Ti-15Al alloys, the
etchant had to be diluted to obtain optimum
etching conditions.
Results and Discussions:
Potentiodynamic Polarization
The nature of stabilization of free corrosion
potential (Ecorr) was similar for all the materials.
Fig 2: Potentiodynamic polarization curves for
The potential moved towards noble potential CP Titanium, Ti-15Al, Ti-13.4Al-29Nb,
on immersion and stabilized in a relatively Ti 13Nb-13Zr and 316L in Hanks solution at
short period of time. However, the stabilization pH 7.4 and 37 C.

66
 Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment

The nature of polarization curves indicated that 15Al, were comparable (Table 1). Addition of
all the alloys passivated immediately on aluminum in significant amount, i.e. 15%,
immersion in the solution. The polarization significantly lowered the breakdown potential
behavior can be termed as stable passivity. This of titanium. The lowest breakdown potential,
behavior was noted for all the samples. The much lower compared to the Ti alloys, was
passivation parameters like breakdown exhibited by 316L steel (37 mV vs SCE). The
potential (Eb), passive current density (ipass) and passive range of all the Ti alloy investigated
the passivation range (Eb-ZCP) were estimated were comparable. The 316L steel exhibited a
Table 1: Passivation parameters obtained from the potentiodynamic polarization curves
in Hanks solution at pH 7.4 and 37 C.

from the polarization curves and they are
tabulated in Table 1. The zero current potential
(ZCP), obtained from the potentiodynamic
polarization curves, of all Ti-alloys was in the
range of 200 600 mV.
Passive current densities were obtained around
the middle of the passive range (Table 1). The
passive current densities of the alloys
investigated were of the same order of
magnitude (1.0 to 8.5 A/cm2). There was no
drastic effect of replacing V in Ti-6Al-4V with
of 2.5%Fe, 4%Fe and 4%Nb. The passive
current densities for the titanium alloys were
comparable (Table 1). The breakdown
potential (Eb) of the Ti alloys, excepting Ti-
low passive range of about 319 mV, when
compared to that of the Ti alloys (1300 to1890
mV).
Corrosion Rates
The Tafel plots for the alloys have been
presented in Fig 3 and 4. The zero current
potential, the cathodic (c) and anodic (a) Tafel
slopes, the estimated corrosion current
densities (icorr) and corrosion rates are tabulated
in Table 2. The corrosion rates of the Ti alloys
were comparable. The reproducibility of the
Tafel plots was relatively poor in the case of
Ti-13Nb-13Zr and therefore, the Tafel
experiments were performed four times

67
 Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*

Table 2: Corrosion rates determined by Tafel extrapolation method.

In two of these experiments, the Ti-13Nb-13Zr
alloy exhibited very low corrosion rates,
almost an order of magnitude lower than the
rate reported in Table 2. In case of Ti-13Nb-
13Zr, the corrosion products of the minor
alloying elements, niobium and zirconium
have to be also considered in addition to
titanium. It has been reported that modification
of passive TiO2 layer by niobium oxide (Nb2O3)
or zirconium oxide (ZrO2) reduces Cl- ingress
into the oxide layer thereby improving the
structural integrity of the oxide film such that
pit initiation events were reduced (13). The Ti-
13Nb-13Zr alloy also possesses sufficient
alpha phase fraction to provide the necessary
mechanical properties (14). The presence of
strong passivating elements like Zr and Nb in
sufficient amounts and their uniform
distribution can also be probable reasons for
the superior corrosion resistance exhibited by
this alloy in some cases.

68
 Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
Fig 3:Tafel plots for CP Titanium, Ti-5Al-2.5Fe,
Ti-6Al-4V, Ti-6Al-4Fe, Ti-6Al-4Nb and 316L
in Hanks solution at 37 C.
Fig 4: Tafel plots for CP Titanium, Ti-15Al, Ti-
13.4Al-29Nb, Ti-13Nb-13Zr and 316L
in Hanks solution at 37 C.
316L steel exhibited a high corrosion rate but
was comparable to that of Ti-alloys. The 316L
stainless steel is susceptible to pitting corrosion
in the presence of chloride ions. The ability of
316L stainless steel to repassivate in biological
environments is also considerably lower
compared to other biomaterials (4). The most
significant difference between 316L stainless
steel and titanium alloys was the absence of a
large passive region in 316L stainless steel.
The anodic polarization curve for 316L
69
posessed a positive slope indicating that the
passive/oxide film was not truly protecting the
material from corrosion even in the passive
region. The passive range was also relatively
small and transition to transpassive region
occurs at a fairly active potential (Fig 4). It
has been reported that this material does not
exhibits a protection potential, and if it does
the hysteresis is large enough to indicate that
the material is not capable of repassivating
quickly if any damage occurs to the passive
surface layer (15). Moreover, corrosion rates
of 316L alloy increase significantly when
subjected to crevice and/or fretting conditions
(16) within the range of clinically relevant
potential-pH combinations and hence this
material is, at best, biotolerant. The results of
the present study confirm the relatively inferior
corrosion resistance of 316L stainless steels
compared to titanium alloys.
Microstructural Characterization
The surfaces that were electrochemically
characterized were microstructurally analyzed.
In the microstructures that would be presented,
beta phase appears dark and the alpha phase
light. The beta phase volume fraction was
calculated for all the Ti alloys. The
microstructures of the alloys are presented in
Figure 5. The results of microstructural
analysis are tabulated in Table 3. Equiaxed
recrystallized grains of alpha was evident in
microstructure of CP titanium (Fig. 5a). The
alpha grain boundaries were quite regular
which suggested that the material may have
been cold rolled and annealed in the alpha
region. A typical cast structure was observed
in the Ti-alloy containing 15% aluminum (Fig.
5b). The fraction of beta phase in Ti-15Al was
higher compared to CP titanium.
 Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*

Table 3: Estimated beta volume fraction in the Titanium alloys utilized in this study.

(a) (b)

(c) (d)

Fig 5: Optical micrographs of (a) CP titanium and (b) Ti-15Al (c) Ti-6Al-4V (d) Ti-6Al
4Nb. The microstructures were obtained on the area used for electrochemical testing in
simulated body fluid solution at 37 C and 7.4 pH

70
 Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
The alloys Ti-6Al-4V, Ti-6Al-4Nb, Ti-6Al-4Fe
and Ti-5Al-2.5Fe possessed a two-phase
alpha-beta structure (Fig 5c, 5d, 5e and 5f,
respectively). Vanadium, niobium and iron are
beta stabilizers. Aluminum is an alpha
stabilizer. Alpha is the dominant phase in all
these alloys as evident from the
microstructures. It has been reported that,
owing to a two-phase equiaxed microstructure,
Ti-6Al-4V is more susceptible to corrosion as
the compositional difference across the grain
boundaries increases which leads to the
galvanic cell formation (17). The structure of
Ti-6Al-4V was fairly fine grained with a grain
size of 22.4 m (Fig. 5c). Addition of niobium
increased the grain size considerably as evident
from Fig 5d. This is a typical Widmanstatten
type of structure. Grain boundary alpha can
also be seen in the microstructure in a
transformed beta matrix. The plate like alpha
precipitates that nucleate and grow below the
beta transus, produce the Widmanstatten
structure.15 The plates often precipitate in
colonies of the same crystallographic
orientation, as can be noticed in Fig. 5d,
because of autocatalytic nucleation (14). The
volume fraction of beta phase in Ti-6Al-4Nb
was almost similar to the other alpha-beta
alloys (Table 3). The Ti-5Al-2.5Fe alloy, a
near alpha-beta alloy, contained a lower
fraction of beta than other alpha-beta alloys.
Figure 5e and 5f show the microstructures of
Ti-6Al-4Fe and Ti-5Al-2.5Fe, respectively.
The grain size of the two alloys were
comparable. However, the volume fraction of
beta phase was higher in case of Ti-6Al-4Fe.
This alloy exhibited a lamellar structure, with
a coarse grain size of 635 m. The alpha phase
appeared to be fine needle shaped (acicular
alpha). The Ti-5Al-2.5Fe alloy also possessed
a coarse grained structure (735m). Blocky
and fine plate like acicular alpha and
71
transformed beta (dark) and alpha at prior beta
grain boundaries could also be seen in the
micrograph of Ti-5Al-2.5Fe (Fig 5f).
A two phase (alpha+beta) with prior beta grain
boundaries were observed in the
microstructure of Ti-13.4Al-29Nb (Fig 5g).
The microstructure of Ti-13Nb-13Zr (Fig 5h)
revealed extremely fine elongated primary
alpha in beta matrix. Its structure, as is evident
from the micrograph is fibrous in nature. It has
been suggested that this structure may result
in better fixing of the implant material with
the tissues (18). Moreover, the reported
enhanced ductility coupled with high strength
of this material may be due to the elongated
primary alpha (white) seen in the
microstructure (Fig 5h) (14). Ti-13Nb-13Zr,
which exhibited low corrosion rates in some
Tafel experiments, possessed the maximum
fraction of beta phase.
Conclusion:
The electrochemical behavior of several Ti-
based alloys (CP Titanium, Ti-15Al, Ti-5Al-
2.5Fe, Ti-6Al-4V, Ti-6Al-4Fe, Ti-6Al-4Nb, Ti-
13.4Al-29Nb, Ti-13Nb-13Zr) and 316L
stainless steel was investigated in simulated
body fluid solution (Hanks solution) at 37C.
All materials exhibited stable passive
polarization behavior. Corrosion rates of the
investigated materials were calculated using
the Tafel extrapolation method. The
stabilization of free corrosion potential was
similar for all the materials excepting Ti-13Nb-
13Zr in some experiments. The corrosion rate
was not affected by the amount of Fe
substitution in Ti-6Al-4V in place of
V. Addition of only Al to Ti was detrimental
to the passivity of titanium. The Ti-15Al alloy
exhibited a lower breakdown potential as
compared to other Ti alloys. The passive
range was low for 316L steel (319 mV), when
 Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*

compared to that of the Ti alloys (1300 to 1890 Acknowledgment:

mV). Moreover, the breakdown potential for
The authors thank Dr. D. Banerjee, Director,
316L was lower compared to the Ti alloys. The
Defence Metallurgical Research Laboratory,
corrosion rates of the Ti alloys was comparable
Hyderabad, India for providing the alloys used
to that of 316L steel. In some cases Ti-13Nb-
in the study. R B acknowledges the equipment
13Zr exhibited very low corrosion rates.
(potentiostat) grant by Alexander von
Hamboldt Foundation.

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