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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.
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Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
65
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.
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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 low passive range of about 319 mV, when
tabulated in Table 1. The zero current potential compared to that of the Ti alloys (1300 to1890
(ZCP), obtained from the potentiodynamic mV).
polarization curves, of all Ti-alloys was in the
Corrosion Rates
range of 200 600 mV.
The Tafel plots for the alloys have been
Passive current densities were obtained around presented in Fig 3 and 4. The zero current
the middle of the passive range (Table 1). The potential, the cathodic (c) and anodic (a) Tafel
passive current densities of the alloys slopes, the estimated corrosion current
investigated were of the same order of densities (icorr) and corrosion rates are tabulated
magnitude (1.0 to 8.5 A/cm2). There was no in Table 2. The corrosion rates of the Ti alloys
drastic effect of replacing V in Ti-6Al-4V with were comparable. The reproducibility of the
of 2.5%Fe, 4%Fe and 4%Nb. The passive Tafel plots was relatively poor in the case of
current densities for the titanium alloys were Ti-13Nb-13Zr and therefore, the Tafel
comparable (Table 1). The breakdown experiments were performed four times
potential (Eb) of the Ti alloys, excepting Ti-
67
Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*
In two of these experiments, the Ti-13Nb-13Zr structural integrity of the oxide film such that
alloy exhibited very low corrosion rates, pit initiation events were reduced (13). The Ti-
almost an order of magnitude lower than the 13Nb-13Zr alloy also possesses sufficient
rate reported in Table 2. In case of Ti-13Nb- alpha phase fraction to provide the necessary
13Zr, the corrosion products of the minor mechanical properties (14). The presence of
alloying elements, niobium and zirconium strong passivating elements like Zr and Nb in
have to be also considered in addition to sufficient amounts and their uniform
titanium. It has been reported that modification distribution can also be probable reasons for
of passive TiO2 layer by niobium oxide (Nb2O3) the superior corrosion resistance exhibited by
or zirconium oxide (ZrO2) reduces Cl- ingress this alloy in some cases.
into the oxide layer thereby improving the
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Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
69
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
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Electrochemical Behavior of Ti-Based Alloys in Simulated Human Body Fluid Environment
The alloys Ti-6Al-4V, Ti-6Al-4Nb, Ti-6Al-4Fe transformed beta (dark) and alpha at prior beta
and Ti-5Al-2.5Fe possessed a two-phase grain boundaries could also be seen in the
alpha-beta structure (Fig 5c, 5d, 5e and 5f, micrograph of Ti-5Al-2.5Fe (Fig 5f).
respectively). Vanadium, niobium and iron are
A two phase (alpha+beta) with prior beta grain
beta stabilizers. Aluminum is an alpha
boundaries were observed in the
stabilizer. Alpha is the dominant phase in all
microstructure of Ti-13.4Al-29Nb (Fig 5g).
these alloys as evident from the
The microstructure of Ti-13Nb-13Zr (Fig 5h)
microstructures. It has been reported that,
revealed extremely fine elongated primary
owing to a two-phase equiaxed microstructure,
alpha in beta matrix. Its structure, as is evident
Ti-6Al-4V is more susceptible to corrosion as
from the micrograph is fibrous in nature. It has
the compositional difference across the grain
been suggested that this structure may result
boundaries increases which leads to the
in better fixing of the implant material with
galvanic cell formation (17). The structure of
the tissues (18). Moreover, the reported
Ti-6Al-4V was fairly fine grained with a grain
enhanced ductility coupled with high strength
size of 22.4 m (Fig. 5c). Addition of niobium
of this material may be due to the elongated
increased the grain size considerably as evident
primary alpha (white) seen in the
from Fig 5d. This is a typical Widmanstatten
microstructure (Fig 5h) (14). Ti-13Nb-13Zr,
type of structure. Grain boundary alpha can
which exhibited low corrosion rates in some
also be seen in the microstructure in a
Tafel experiments, possessed the maximum
transformed beta matrix. The plate like alpha
fraction of beta phase.
precipitates that nucleate and grow below the
beta transus, produce the Widmanstatten Conclusion:
structure.15 The plates often precipitate in The electrochemical behavior of several Ti-
colonies of the same crystallographic based alloys (CP Titanium, Ti-15Al, Ti-5Al-
orientation, as can be noticed in Fig. 5d, 2.5Fe, Ti-6Al-4V, Ti-6Al-4Fe, Ti-6Al-4Nb, Ti-
because of autocatalytic nucleation (14). The 13.4Al-29Nb, Ti-13Nb-13Zr) and 316L
volume fraction of beta phase in Ti-6Al-4Nb stainless steel was investigated in simulated
was almost similar to the other alpha-beta body fluid solution (Hanks solution) at 37C.
alloys (Table 3). The Ti-5Al-2.5Fe alloy, a All materials exhibited stable passive
near alpha-beta alloy, contained a lower polarization behavior. Corrosion rates of the
fraction of beta than other alpha-beta alloys. investigated materials were calculated using
Figure 5e and 5f show the microstructures of the Tafel extrapolation method. The
Ti-6Al-4Fe and Ti-5Al-2.5Fe, respectively. stabilization of free corrosion potential was
The grain size of the two alloys were similar for all the materials excepting Ti-13Nb-
comparable. However, the volume fraction of 13Zr in some experiments. The corrosion rate
beta phase was higher in case of Ti-6Al-4Fe. was not affected by the amount of Fe
This alloy exhibited a lamellar structure, with substitution in Ti-6Al-4V in place of
a coarse grain size of 635 m. The alpha phase V. Addition of only Al to Ti was detrimental
appeared to be fine needle shaped (acicular to the passivity of titanium. The Ti-15Al alloy
alpha). The Ti-5Al-2.5Fe alloy also possessed exhibited a lower breakdown potential as
a coarse grained structure (735m). Blocky compared to other Ti alloys. The passive
and fine plate like acicular alpha and range was low for 316L steel (319 mV), when
71
Animesh Choubey1, Bikramjit Basu* and R. Balasubramaniam*
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