Materials Characterization 49 (2002) 73 79

Characterization of different materials for corrosion

resistance under simulated body fluid conditions
I. Gurappa*
Surface Engineering Group, Defence Metallurgical Research Laboratory, Kanchanbagh PO, Hyderabad 500 058, India
Received 27 March 2002; received in revised form 14 September 2002; accepted 17 September 2002

Abstract

A systematic characterization study has been carried out on different materials such as commercial purity
titanium, Ti 6Al 4V, 316L stainless steel, and a cobalt-based alloy under simulated body fluid conditions at
37
C. Breakdown potential, corrosion rates, pitting/crevice corrosion resistance, and the ability to form
protective oxide scales were evaluated and compared. The advantages of the titanium alloy over other
materials were highlighted. An attempt has also been made to study the suitability of titanium alloy, IMI 834,
for biomedical applications. AC impedance measurements were also carried out in order to provide supportive
evidence for the above results.
D 2002 Elsevier Science Inc. All rights reserved.

Keywords: Titanium; Cobalt-based alloy; Simulated body fluid conditions; Corrosion resistance

1. Introduction human body is that it should be biocompatible and

Biomedical materials play an important and a
critical role in manufacturing a variety of prosthetic
devices in a modern world. Prosthetic devices are
artificial replacements that are used in a biological
system, such as the human body in an effort to
provide the function of the original part. These
devices are generally made of polymeric, metallic
and ceramic materials, or combinations of these
materials, depending on the intended use. Metals/
alloys are used as surgical implants in the human
body primarily for orthopedic purposes. The first
requirement for any material to be placed in the
* Tel.: +91-40-458-6515; fax: +91-40-434-1439.
E-mail address: igp1@rediffmail.com (I. Gurappa).
not cause any adverse reaction in the body. The
material must withstand the body environment and
not degrade to a point that it cannot function in the
body as intended.
Corrosion of metal implants is critical because it
can adversely affect the biocompatibility and mech-
anical integrity. The materials used should not cause
any adverse biological reaction in the body and
simultaneously, it must be stable and retain its func-
tional properties. Corrosion and surface oxide film
dissolution are the two mechanisms for introducing
additional ions into the body. Extensive release of
ions from prosthesis can result in adverse biological
reactions and can lead to mechanical failure of the
device.
Metals/alloys used in the human body must have a
high corrosion resistance and must not be treated or
used in a configuration that would degrade the
corrosion behavior. Degradation of metals and alloys

1044-5803/02/$ see front matter D 2002 Elsevier Science Inc. All rights reserved.
PII: S 1 0 4 4 - 5 8 0 3 ( 0 2 ) 0 0 3 2 0 - 0
74 I. Gurappa / Materials Characterization 49 (2002) 7379
used as surgical implant orthopedic devices is usually
a combination of electrochemical and mechanical
effects. Modern-day life has resulted in the increased
use of implants at a younger age. The average life
span has also been increased. Both these factors
necessitated the use of materials with enhanced life
and/or innovation of newer implant materials with
prolonged life.
Corrosion is the first consideration for a material
of any type that is to be used in the body because
metal ion release takes place mainly due to corrosion
of surgical implants [1]. Therefore, various in vitro
and in vivo tests have to be carried out in order to
identify appropriate materials for use as surgical
implants. It is desirable to keep the metal ion release
to a minimum by the use of corrosion-resistant
materials. Some effects of incompatible materials
include interference with normal tissue growth near
the implant, interference with systematic reactions of
the body, and transport and deposition of metal ions
at selective sites or organs may occur [2 5]. There is
always a concern about the carcinogenic effects of
foreign materials in the body both short- and long-
term periods exceeding 20 years. Some individuals
are sensitive to metals and some develop metal
sensitivity later after receiving an implant.
The environment of the body is extremely well
buffered so that the pH is maintained at around 7.4
and it is, of course, held at 37
C. Two features
control the severity of this environment. Firstly, the
saline solution is an excellent electrolyte and facili-
tates the electrochemical mechanisms of corrosion
and hydrolysis. Secondly, there are many molecular
and cellular species in the tissues that have the
ability to catalyze certain chemical reactions or
rapidly destroy certain components identified as
foreign. Corrosion behavior of materials can be
studied either in vivo or in vitro using artificial
physiological fluids, in which the oxygen content
is controlled at a suitably low value at 37
C. Hanks
solution is an example of an artificial solution, which
has been used over a period for corrosion testing in
the laboratory [6].
In the present investigation, a systematic study
was carried out in order to understand the stability of
various materials both for short- and long-term bio-
medical applications and thereby suggest an appro-
priate material for surgical implants.
2. Experimental
Different materials tested in the present investiga-
tion are provided in Table 1.
The corrosion resistance of different materials
that are being used and intended to use as bioma-
Table 1
Different metallic materials tested for biomedical
applications
Material Type Chemical
composition (wt.%)
Stainless AISI 316L 18 Cr, 12 Ni,
steel 2.5 Mo, < 0.03 C,
and balance iron
Cobalt Co Ni Cr Mo 35 Ni, 35 Co,
alloys 20 Cr, and 10 Mo
Titanium Commercial 99.6%
purity (0.10 C and 0.3 Fe)
Titanium Ti 6Al 4V 6 Al, 4 V,
alloys and balance titanium
IMI 834 5.8 Al, 4 Sn,
3.6 Zr, 0.7 Nb,
0.54 Mo, 0.32 Si,
and balance titanium
terials were tested by using various electrochemical
techniques in de-aerated Hanks solution of pH 7.4
(Table 2), known to simulate body fluid envir-
onment [6,8,9], at 37
C (98.4
F), which is equi-
valent to human body temperature [6 9]. The
accuracy of temperature maintained in the present
investigation is 1
C. Disc specimens of 14 mm
diameter and 4 mm height were machined from the
corresponding alloy ingots, polished up to 800 grit
surface, washed with distilled water followed by
acetone before testing the materials. A potentiostat,
model 273A, in association with corrosion analysis
software supplied by EG&G PARC, USA, was used
to test different materials. A standard three-electrode
cell in which graphite is the counter-electrode and
saturated calomel electrode is the reference electrode
was used. The total amount of solution taken in the
cell is about 600 ml. Argon gas was used for de-
aeration of the electrolyte. For recording impedance
plots, the above potentiostat in association with
impedance software was used.
Potentiodynamic tests were carried out to deter-
mine the breakdown potentials as well as corrosion
rates of different materials. The isolated electrode
potentials as a function of time plots were used to
assess the ability of various materials to form a
protective oxide scale on their surfaces upon immer-
sion in the simulated body fluid environment. A
cyclic polarization technique was used to evaluate
pitting and crevice corrosion resistance of various
materials. AC impedance plots were used to provide
supportive evidence to the above studies. Finally,
scanning electron microscopy (SEM) was used to
understand the surface morphology of the titanium
alloys, Ti 6Al 4V and IMI 834, after corrosion
studies. The corrosion morphology of titanium
 I. Gurappa / Materials Characterization 49 (2002) 7379 75

Table 2 Table 3
The composition of Hanks solution Breakdown potentials and corrosion rates of different
Compound Composition (g/l) materials in de-aerated Hanks solution at 37
C
NaCl 8.00 Material Breakdown Corrosion rate
KCl 0.40 potential (V) (mils/year)
CaCl2 0.14 316L stainless steel 0.28 0.17
NaHCO3 0.35 Cobalt alloy 0.6 0.056
Na2HPO4
2H2O 0.06 Ti 6Al 4V 1.9 0.007
KH2PO4 0.60
MgSO4
7H2O 0.06
MgCl2
6H2O 0.10 requirement is to determine the breakdown potential,
Glucose 1.00 i.e., at which potential the passive film breaks down.
For selecting any material for biomedical application,
alloys, Ti 6Al 4V and IMI 834, was studied by the breakdown potential plays a major role.
SEM. Table 3 illustrates breakdown potentials measured
in de-aerated Hanks solution at 37
C for various
materials. As can be seen, the maximum breakdown
3. Results potential is observed for the titanium alloy, Ti 6Al
4V, and followed by the cobalt alloy. The minimum
Determination of the chemical interaction of breakdown potential is observed for 316L stainless
metallic materials/bone prosthesis with the body fluid steel. The corrosion rates of different materials were
environment is essential in order to understand their evaluated and are presented in Table 3. The maximum
stability in the human body. One simple way to study corrosion rate was observed for the 316L stainless
the film formation and passivation of implants/alloys steel followed by the cobalt alloy. The minimum
in a solution is to monitor the open-circuit electrode corrosion rate is observed for the titanium alloy, Ti
potential as a function of time. A rise of potential in 6Al 4V. In essence, the Ti 6Al 4V alloy exhibits
the positive direction indicates the formation of a the minimum corrosion rate and maximum break-
passive film, and a steady potential indicates that the down potential when compared to other materials.
film remains intact and protective. A drop of potential Another most important requirement is the pitting
in the negative direction indicates breaks in the film, and crevice corrosion resistance. Any metal/alloy
dissolution of the film, or no film formation. An intended for use as a biomaterial should exhibit
open-circuit potential as a function of time for differ- excellent pitting and crevice corrosion resistance.
ent materials tested in the present investigation is This can be determined by carrying out cyclic polar-
provided in Fig. 1. As can be seen, the potential ization experiments in Hanks solution at 37
C. The
shifted in the positive direction for all the tested cyclic polarization curves recorded for various mate-
materials, which clearly indicates the formation of a rials in de-aerated Hanks solution at 37
C are
passive film on their surfaces. Then, the second presented in Fig. 2. No hystersis loop is observed

Fig. 1. Open-circuit electrode potential as a function of time for various materials in de-aerated Hanks solution at 37
C.
76 I. Gurappa / Materials Characterization 49 (2002) 7379

Fig. 2. Cyclic polarization plots of different materials in de-aerated Hanks solution at 37
C.

for cobalt and titanium alloys. In the case of 316L
stainless steel, the reverse scan takes an entirely
different path when compared to the forward scan.
This clearly indicates that the titanium and cobalt
alloys have excellent pitting and crevice corrosion
resistance, while 316L stainless steel is highly sus-
ceptible to pitting and crevice corrosion.
With a view to understanding the suitability of a
recently developed titanium alloy, IMI 834, for bio-
medical applications, studies were carried out on IMI
834. It was observed that the alloy forms a protective
oxide scale on its surface upon immersion in a
simulated body fluid environment and exhibits a very
low corrosion rate and good breakdown potential.
The corrosion morphology observed under the SEM
was found to be similar to that of the normally used
titanium alloy, Ti 6Al 4V (Fig. 3). In both cases,
grooves and ridges typical for titanium alloy surfaces
were observed. Further, no corrosion pits are seen on
the surfaces of both the alloys under simulated body
fluid environmental conditions. This indicates that the
alloy is suitable for biomedical applications. How-
ever, further studies are essential before using it for
biomedical applications.
Impedance measurements are one of the most
useful and informative methods of corrosion assess-
ment [10 15]. The response of a corroding specimen
to an applied small amplitude signal will depend on
the frequency of the signal. The magnitude and phase
shift at each frequency is noted, and the corrosion cell
response is expressed as a combination of resistive,
capacitive, and inductive components. The imped-
ance behavior of a specimen can be expressed either
in Bode plots of impedance modulus (|Z|) as a
function of frequency or in Nyquist plots of Z00(w)
as a function of Z0(w), where w = 2pf. The Nyquist
plot shows semicircle, with increasing frequency in a
counterclockwise direction. At very high frequency,

Fig. 3. SEM photographs of titanium alloys, Ti 6Al 4V and IMI 834, showing similar corrosion morphology after corrosion
studies in de-aerated Hanks solution at 37
C.
 I. Gurappa / Materials Characterization 49 (2002) 7379
Fig. 4. Nyquist plots for various biomaterials in de-aerated Hanks solution at 37
C.
the imaginary component (Z00) disappears, leaving
only the solution resistance, RV. At very low fre-
quency, Z00 again disappears, leaving a sum of RV and
the faradic reaction resistance or polarization resist-
ance, Rp. Because of this behavior, measurements
taken at high frequencies will generally reveal the
solution resistance, while measurements taken at low
frequencies will measure both solution resistance and
charge transfer resistance. Thus, the difference
between low and high frequencies gives the charge
transfer resistance, which is inversely proportional to
the corrosion rate. AC impedance plots recorded for
different biomaterials in Hanks solution at 37 1
C
are provided in Fig. 4. The charge transfer resistance
measured with the help of Nyquist plots clearly
confirms the superior performance of the titanium
alloy followed by cobalt and 316L stainless steel by
the increasing charge transfer resistance in the same
order: titanium alloy < cobalt alloy < 316L stainless
steel.
4. Discussion
Stainless steels predominate as materials for pros-
thetic devices because they are relatively inexpensive
and formable by common techniques. Further, their
mechanical properties are controllable over a wide
range, providing optimum strength and ductility.
However, stainless steels are the least corrosion
resistant over the long term and cause rashes or pain
due to release of nickel ions as evidenced from the
above results. The present results clearly reveal that
the breakdown potential is relatively low over Co and
Ti alloys (Table 3). Further, the breakdown potential
77
decreases with increase in the cold work and the
maximum breakdown potential is observed for the
steel without any cold work [7]. The results on pitting
corrosion of 316L stainless steel showed that it is
susceptible to both pitting and crevice corrosion (Fig.
2). Pitting corrosion is evidenced by observing a
hystersis loop, while crevice corrosion is seen
through the difference in potential between break-
down and protective potentials. From these studies, it
is also very clear that the ability of 316L stainless
steel to repassivate is considerably less compared to
other materials. Stress corrosion cracking may also
occur in vivo in the case of possible film breakdown
and extremely high loads. Therefore, they are better
suited only for temporary components in orthopedic
treatments like bone screws, bone plates, intramodul-
lary rods, and other temporary fixation devices.
Cobalt chromium alloys are important biomate-
rials because of their corrosion resistance (an order of
magnitude greater than stainless steels) and high
mechanical properties [8,9]. Although the cobalt
alloys do not passivate as is the case for titanium
alloys, good resistance against pitting corrosion and
crevice corrosion has been confirmed for cobalt
alloys containing molybdenum as evidenced from
the present results. Therefore, cobalt-based alloys
are widely used safely for the fabrication of various
devices that are surgically implanted in the body.
These devices must be highly reliable because the
failure of certain implants (e.g., heart valves) can be
fatal and the failure of other implants can necessitate
further surgery. They are also used in total knee
replacements and, to a lesser extent, as implants that
fix bone fractures like bone screws, staples, and
plates. The support structures for heart valves are
78 I. Gurappa / Materials Characterization 49 (2002) 7379
also often fabricated from cobalt-based alloys. A
variety of dental implants have also been produced
from cobalt alloys.
5. Advantages of titanium and its alloys
Titanium possesses three outstanding character-
istics for biomedical applications. They are
(a) corrosion resistance in tissue,
(b) absence of tissue toxicity and allergic reactions,
and
(c) good strength, a factor for the safety of the device
and low elastic modulus, which appears desirable
for reducing stress-shielding effects of bone due
to the presence of the implant.
The corrosion resistance of titanium and its alloys
is obtained due to the formation of a stable oxide
scale on their surfaces. It can reform if damaged in
physiological fluids at body temperature. A variety
of titanium alloys have been developed by the
addition of different alloying elements. However,
only Ti 6Al 4V alloy and four grades of commer-
cially available pure titanium are customarily used in
the body. Pure titanium is used in cases where there
is low mechanical load on the implant, while Ti
6Al 4V alloy is used where good mechanical load is
there.
Ti 6Al 4V alloy offers the best combination of
properties of all structural implant materials today as
evidenced from its maximum breakdown potential,
minimum corrosion rate, and high resistance to pit-
ting and crevice corrosion. This alloy has a much
greater yield and ultimate strength than pure titanium.
It is generally produced by forging, but can be cast.
However, release of titanium into adjacent tissue has
been reported upon prolonged exposure. It is believed
that a proper pretreatment before surgery can prevent
this phenomenon [16].
A titanium-based alloy, Ti 5Al 2.5Fe, was dev-
eloped as an implant material, and it was reported that
its mechanical properties are comparable to the exist-
ing alloy, Ti 6Al 4V, and safe for human use.
Various titanium alloys with different alloying ele-
ments were studied for their corrosion resistance [17].
The modified titanium-based alloys, Ti 15%Zr
4%Nb 2%Ta and Ti 15%Sn 4%Nb 2%Ta
0.2%Pd, with improved biological safety, strength,
and ductility for medical implants were developed
[18,19]. These alloys were reported to exhibit super-
ior properties over that of Ti 6Al 4V extra low
interstitial (ELI) alloy since Ti 6Al 4V ELI has
created recent concerns due to the suspected effects
of aluminium (Al) and vanadium (V). The presence
of Al ions results in phosphorus deficiency in blood
and bone due to the combination of Al with inorganic
phosphorus while vanadium causes cytotoxicity.
6. Future research
The corrosion behavior of several existing materi-
als used today is not ideal in all respects. Although a
small number of biomaterials have been in use, post-
healing surgery is essential in order to remove the
implanted material. Further, the implant is obviously
an item for which complete resistance of the metal
should be aimed at throughout the period of use.
Therefore, it is essential to develop a material that can
satisfy all the required properties over the stipulated
period and then start degrading in the body itself
without further surgery. In fact, it is a real challenge
to scientists and surgeons and has tremendous poten-
tial for future research. This will direct the attention
to the development of an excellent biocompatible and
biodegradable polymeric material, which will cer-
tainly be a smart material and thereby eliminate costly
post-healing operations.
Acknowledgements
The Defence Research and Development Organ-
isation is gratefully acknowledged for financial
assistance.
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