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Comparison of fretting corrosion behaviour of
Ti6Al4V alloy and CP-Ti in Ringers solution
B. Sivakumar, S. Kumar and T. S. N. Sankara Narayanan*
The fretting corrosion behaviour of Ti6Al4V alloy in Ringers solution was evaluated and
compared with that of commercially pure titanium (CP-Ti). Free corrosion potential, morphology of
the fretted zone, extent of formation and accumulation of debris and wear volume were used as
parameters of evaluation. Both Ti6Al4V alloy and CP-Ti behave similarly in terms of change in
free corrosion potential as a function of time, morphological features and wear mechanism. Ti
6Al4V alloy, however, exhibits an increase in corrosion susceptibility, decrease in tendency for
repassivation, higher amount of formation and accumulation of debris and an increase in wear
volume compared with CP-Ti. The study points out the importance of material selection for
implants that would encounter fretting corrosion.
Keywords: Tribocorrosion, Fretting corrosion, Ti and its alloys, Implant, Joint prostheses, Repassivation
Introduction
Titanium and its alloys are widely used as orthopaedic
and dental implants due to their low density, better
mechanical properties, very high strength/weight ratio
(specic strength), excellent corrosion resistance and
biocompatibility.
15
Among the various types of Ti
alloys, Ti6Al4V alloy has been the choice in many
instances because its mechanical properties and corrosion
resistance are ideal for implant applications. Studies on
the corrosion and biocompatibility aspects of Ti and its
alloys performed in vitro proved that the passive oxide
layer is stable and offers excellent corrosion protection
and biocompatibility.
15
Implant retrieval analysis, how-
ever, reveals discolouration of the implant and accumula-
tion of metal ions on tissues beside the implant.
6
The
inferior mechanical properties of the naturally formed
passive oxide layer that could be disrupted at very low
shear stresses, even by rubbing against soft tissues, are
considered responsible for such an occurrence.
7
Owing to
the inherent property of titanium and its alloys, the
passive oxide layer could subsequently reform upon
reaction with the local environment. However, implant
retrieval analysis conrms that the capability of restora-
tion of the damaged passive lm is not instantaneous, as it
is generally believed.
Fretting corrosion is the deterioration of a material
that occurs at the interface of two contacting surfaces
due to small oscillatory movements in the presence of a
corrosive medium. Manufacturing of implant materials,
though involves a component geometry specic locking
mechanism, micromotion do occur,
8
which enables the
penetration of the body uid into this junction and
facilitates mechanically assisted crevice and fretting
corrosion.
9,10
The modular interfaces of total joint
prosthesis, mainly at the xation of the implant stem
bone or cement, are subjected to micromotion (,100
mm) that could result in fretting corrosion.
11,12
The
fretting corrosion behaviour of untreated and surface
modied titanium and its alloys was studied by many
researchers.
1320
These studies conrm the following
observations:
(i) removal of the passive oxide layer induced by
fretting
(ii) formation and entrapment of debris at the
fretted zone, though most of them are pushed
away towards edges
(iii) increase in wear volume if the debris possesses
an abrasive character
(iv) delay in repassivation after the fretting motion
is ceased.
The fretting corrosion behaviour of Ti and its alloys
could be different in terms of the nature of the passive
lm, susceptibility for corrosion upon removal of the
passive lm, hardness of the alloy, extent of fretting
wear, abrasive nature of the oxide debris, rate of
corrosion and leaching of alloying elements. Such a
comparison will be of much help to choose the right type
of material for implants that would encounter fretting
corrosion. In this perspective, the present work aims to
evaluate the fretting corrosion behaviour of Ti6Al4V
alloy in Ringers solution and compare it with that of
commercially pure titanium (CP-Ti).
Experimental
Commercially pure titanium (grade 2) [with the chemi-
cal composition of Ti0?01N0?03C0?01H0?20Fe
0?18O (wt-%)] and Ti6Al4V alloy (grade 5) [with the
chemical composition of Ti0?02N0?03C0?011H
0?22Fe0?16O6?12Al3?93V (wt-%)] discs of 20 mm in
Metallurgical Laboratory, Madras Centre, CSIR Complex, Taramani,
Chennai 600 113, India
*Corresponding author, email tsnsn@rediffmail.com
;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;
2011 W. S. Maney & Son Ltd
Received 3 September 2011; accepted 12 October 2011
158 Tribology 2011 VOL 5 NO 4 DOI 10.1179/1751584X11Y.0000000020
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diameter and 2 mm in thickness were used as substrate
materials. They were mechanically polished using
various grades of SiC paper followed by 0?3 mm
diamond paste to a mirror nish, rinsed with deionised
water and dried using a stream of compressed air.
Fretting corrosion experiments were performed using a
fretting corrosion test assembly. The details of the test
assembly have already been discussed in our earlier
papers.
1720
A ball on at contact conguration that
involves a 8 mm w alumina ball (nish, G 10 grade;
hardness, 1365 HV) moving against the stationary CP-
Ti/Ti6Al4V alloy at was chosen so that large contact
stresses could be achieved under very low loads.
Normal loads of 3 and 10 N, oscillating frequencies of
5 and 10 Hz and linear peak to peak displacement
amplitude of 180 mm were used as the fretting corrosion
test parameters. The Hertzian contact pressures for the
loads used (3 and 10 N) will be ,500 and 1200 MPa.
The tests were performed for 18 000 (5 Hz) and 36 000
(10 Hz) fretting cycles. The test parameters employed in
this study imply a gross slip condition. Ringers solution,
having a chemical composition (in g L
21
) of 9NaCl
0?24CaCl
2
0?43KCl0?2NaHCO
3
(pH 7?8) at 310 K,
was used as the electrolyte solution. The CP-Ti/Ti
6Al4V alloy discs subjected to fretting corrosion
formed the working electrode, while a saturated calomel
electrode (SCE) and a graphite rod served as reference
and auxiliary electrodes respectively. These electrodes
were placed in the fretting corrosion cell in such a way
that only 2 cm
2
area of the working electrode was
exposed to the Ringers solution. The alumina ballCP-
Ti/Ti6Al4V alloy at contact was arranged in such a
way that they were totally immersed in the Ringers
solution. The fretting corrosion cell was connected to
a potentiostat/galvanostat/frequency response analyser
from ACM Instruments (model Gill AC) to measure the
free corrosion potential (FCP) of CP-Ti/Ti6Al4V
alloy as a function of time. Before the onset of fretting,
CP-Ti/Ti6Al4V alloy was allowed to stabilise for 1 h
in Ringers solution. The change in FCP of CP-Ti/Ti
6Al4V alloy was monitored as a function of time. The
FCP measurement was repeated at least three times to
ensure reproducibility of the test results. The morpho-
logical features of the fretted zone were assessed using
SEM. Energy dispersive X-ray (EDX) analysis was
performed at selected regions of the fretted zone to
identify their chemical nature. The three-dimensional
(3D) prole of the fretted zone was assessed using an
ultrasonic based non-destructive testing device.
Results and discussion
Fretting corrosion behaviour of Ti6Al4V alloy
Free corrosion potential measurement of Ti6Al4V alloy
The FCP is a qualitative indicator of the corrosion
regime (active or passive), in which a metal resides, and
it has been used to evaluate the performance of Ti and
its alloys under fretting corrosion conditions.
2024
The
change in FCP of Ti6Al4V alloy recorded before the
onset of fretting, with the onset of fretting, during
fretting and after the fretting motion is ceased, is shown
in Fig. 1a. The FCP is a mixed potential, reecting the
state of the unworn material and those in the fretting
wear track. Before the onset of fretting, the FCP of Ti
6Al4V alloy exhibits an anodic shift, suggesting
thickening of the passive lm during the initial
stabilisation period of 1 h. With the onset of fretting, a
sudden drop in FCP (cathodic shift) (Fig. 1a) and
a surge in anodic current (Fig. 1b) are observed. A
similar observation was also made earlier by many
researchers during tribocorrosion of bare and surface
modied Ti, Ti6Al4V alloy and stainless steel in many
environments.
13,14,1723
Komotori et al.
24
have observed
these changes when Ti6Al4V alloy is scratched by a
sapphire ball in Ringers solution. According to
Ponthiaux et al.,
25
the FCP of titanium becomes much
closer to the freshly ground material in the electrolyte
during corrosion wear. The extent of cathodic shift in
FCP and the surge in anodic current observed in the
present study indicates removal of the passive oxide
layer and increase in corrosion susceptibility of Ti6Al
4V alloy in Ringers solution. The increase in applied
load from 3 to 10 N results in a higher cathodic shift in
FCP (Fig. 1a). This is due to the effective removal of the
passive lm that results in a larger active fretted area.
Contu et al.
26
have also observed a similar effect during
the mechanical abrasion of Ti and Ti6Al4V alloy in
inorganic buffer. The increase in frequency, from 5 to
10 Hz, seems to have a relatively lesser inuence than
those caused by the load (Fig. 1a).
1 Change in a FCP and b anodic current of Ti6Al4V alloy measured as function of time (xed condition: amplitude,
180 mm; variables: load, frequency and fretting cycles)
Sivakumar et al. Corrosion behaviour of Ti6Al4V and CP-Ti in Ringers solution
Tribology 2011 VOL 5 NO 4 159
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During fretting, some uctuations in the FCP of Ti
6Al4V alloy are observed following the periodic
removal (depassivation) and growth (repassivation) of
the passive oxide layer in the fretted zone, suggesting the
existence of a dynamic equilibrium between depassiva-
tion and repassivation phenomena.
14,22
The average
values of uctuation in FCP for a load of 3 N are 902
and 1122 mV at 5 and 10 Hz respectively. However,
when the load is increased from 3 to 10 N, the
corresponding values become 662 and 762 mV.
The decrease in the extent of uctuations with the
increase in load indicates the decrease in tendency of
the alloy to repassivate. This can be attributed to the
increase when the load is increased from 3 to 10 N. After
the fretting motion is ceased, the FCP of Ti6Al4V
alloy exhibits an anodic shift, suggesting the occurrence
of repassivation. This is due to the rapid regeneration of
TiO
2
layer in the active areas of the fretted zone
following the reaction of the fresh Ti metal ions with the
dissolved oxygen available in Ringers solution. A
similar behaviour was observed earlier by Komotori
et al.
24
and Ponthiaux et al.
25
during the repassivation of
Ti and Ti6Al4V alloy. During repassivation, two
important factors, such as the ability of the material to
return to the initial steady state potential and the time
required for such an occurrence, should be considered.
Ideally, the potential should reach the initial steady state
before the onset of fretting. After the fretting motion is
ceased, Ti6Al4V alloy attained its initial steady state
potential for a load of 3 N at 5 and 10 Hz. However,
when the load is increased to 10 N, though the FCP
reaches the initial steady state potential, the time taken
for this occurrence becomes relatively higher. The
increase in contact area of the fretted zone and the
2 Morphology of Ti6Al4V alloy after subjecting it to fretting corrosion (conditions: amplitude, 180 mm; frequency,
10 Hz; load, 10 N; fretting cycles, 36 000): a fretted zone (circled area) and surrounding areas (fretting direction is indi-
cated by doubled sided arrow mark); b central region of fretted zone; c debris collected at edges
3 Change in FCP of CP-Ti and Ti6Al4V alloy measured as function of time: a amplitude, 180 mm; load, 3 N; frequency, 5 Hz;
number of fretting cycles, 18 000; b amplitude, 180 mm; load, 10 N; frequency, 5 Hz; number of fretting cycles, 18 000
4 Rate of change in FCP of CP-Ti and Ti6Al4V alloy
measured during repassivation (after fretting motion is
ceased)
Sivakumar et al. Corrosion behaviour of Ti6Al4V and CP-Ti in Ringers solution
160 Tribology 2011 VOL 5 NO 4
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extent of damage at 10 N could be considered respon-
sible for this behaviour.
Surface morphology of fretted zone of Ti6Al4V alloy
The morphology of Ti6Al4V alloy after fretting
corrosion (conditions: amplitude, 180 mm; frequency,
10 Hz; load, 10 N; fretting cycles, 36 000) is shown in
Fig. 2.
The fretted zone (circled region) has experienced
severe damage, whereas the surrounding areas of the
fretted zone are relatively smooth, in which wear debris
is smeared all around (Fig. 2a). The central region of the
fretted zone reveals severe damage due to the extensive
shear deformation and the ploughing action of the
alumina ball, suggesting the involvement of adhesive
galling as the predominant wear mechanism (Fig. 2b).
Microwelding of surface asperities occurs during the
initial stages, whereas the asperities get sheared and
plucked away in the subsequent stages. Redeposition of
the removed material, conrmed by the presence of
debris within the fretted zone (Fig. 2b), enables an
increase in roughness and further accelerates the wear
rate. The debris collected at the edges of the fretted zone
is shown in Fig. 2c. The surface of the Al
2
O
3
ball
counterface reveals the transfer of material from Ti
6Al4V alloy, which conrms the occurrence of adhesive
galling.
Comparison of fretting corrosion behaviour of
CP-Ti and Ti6Al4V alloy
The similarity in shape of the FCPtime curves of CP-Ti
and Ti6Al4V alloy suggests the occurrence of similar
phenomena during fretting corrosion of these materials
(Fig. 3).
5 Comparison of morphologies of a, c, e, g CP-Ti and b, d, f, h Ti6Al4V alloy after subjecting them to fretting corro-
sion (conditions: amplitude, 180 mm; load, 10 N; frequency, 5 Hz; fretting cycles, 18 000): a, b entire fretted zone
(circled region; fretting direction is indicated by double sided arrow mark); c, d central region;
e, f edge region; g, h debris at edges
Sivakumar et al. Corrosion behaviour of Ti6Al4V and CP-Ti in Ringers solution
Tribology 2011 VOL 5 NO 4 161
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In spite of the similarity in trend, some noticeable
differences could be observed. Compared with CP-Ti,
Ti6Al4V alloy exhibits a higher cathodic shift in FCP
with onset fretting, few uctuations during fretting and a
decrease in the rate of anodic shift in FCP after the
fretting motion is ceased. These effects are well
pronounced at 10 N (Fig. 3b). The higher cathodic shift
in FCP signies the increase in susceptibility of Ti6Al
4V alloy for corrosion in Ringers solution. The few
uctuations in FCP indicate the decrease in tendency of
Ti6Al4V alloy to repassivate. Contu et al.
26
have also
reported that CP-Ti displays a better tendency for
repassivation than Ti6Al4V alloy in inorganic buffer
solution at pH 4?0 and 7?0. The delay in cathodic
reaction kinetics can be considered responsible for the
poor tendency for repassivation exhibited by Ti6Al4V
alloy compared with CP-Ti.
27
The rate of change in FCP after the fretting motion is
ceased conrms the decrease in ability of Ti6Al4V
alloy to revert to the initial steady state (Fig. 4). The
time to reach a threshold value of 2550 mV(SCE) is
117 s for CP-Ti, whereas Ti6Al4V alloy under similar
experimental conditions (at 10 N/5 Hz) attains this
threshold only at 672 s.
A comparison of the morphologies of CP-Ti and Ti
6Al4V alloy after subjecting them to fretting corrosion
(conditions: amplitude, 180 mm; load, 10 N; frequency,
5 Hz; fretting cycles, 18 000) is shown in Fig. 5. The
fretted zone (circled region) has experienced severe
damage due to the extensive shear deformation and
ploughing action of the alumina ball (Fig. 5a and b),
suggesting the involvement of adhesive galling as the
predominant wear mechanism in both cases. However,
the central (Fig. 5c and d) and edge regions (Fig. 5e and
f) of the fretted zone reveal that the amount of
formation of debris and their entrapment is relatively
high for Ti6Al4V alloy. In addition, the extent of
accumulation of debris in the edge regions of the fretted
zone is relatively high for Ti6Al4V alloy (Fig. 5g and
h).
The 3D prole of the fretted zone of CP-Ti and Ti
6Al4V alloy, after subjecting them to fretting corrosion
(conditions: amplitude, 180 mm; load, 3 N; frequency,
5 Hz; fretting cycles, 18 000), is shown in Fig. 6a and b
respectively.
It is evident from Fig. 6 that the wear volume is higher
for Ti6Al4V alloy than for CP-Ti under similar
conditions. Masmoudi et al.
28
have pointed out that
6 Three-dimensional prole of fretted zone of a CP-Ti and b Ti6Al4V alloy after fretting corrosion (conditions: ampli-
tude, 180 mm; load, 3 N; frequency, 5 Hz; fretting cycles, 18 000) (X and Y axes: values are in mm; Z axis: values are
in 610
23
mm)
Sivakumar et al. Corrosion behaviour of Ti6Al4V and CP-Ti in Ringers solution
162 Tribology 2011 VOL 5 NO 4
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the wear rate of nitric acid passivated Ti6Al4V alloy is
higher than that of CP-Ti in Ringers solution.
According to them, the lower thickness of the oxide
lm and its inferior resistance to corrosive medium are
responsible for the higher wear rate of Ti6Al4V
alloy.
28
This observation is also supported by other
researchers.
27,29,30
Contu et al.
26
have reported that with
respect to corrosion, both CP-Ti and Ti6Al4V alloy
exhibit similar behaviours during mechanical abrasion
in inorganic buffer, since oxidation of titanium is the
major reaction. The tendency for repassivation, how-
ever, is relatively higher for CP-Ti than for Ti6Al4V
alloy.
26
Martin et al.
31
have suggested that the hardness
of wear debris becomes the controlling factor in
determining the performance of Ti6Al4V alloy under
tribocorrosion conditions. The nanohardness of Ti6Al
4V alloy is ,5?1 GPa, whereas the hardness of its debris
layer is reported to be nearly double.
32
The decrease in ability of Ti6Al4V alloy to revert to
its initial steady state (Fig. 4) could be correlated to the
extent of formation and entrapment of debris at the
fretted zone, the hard and abrasive nature of the debris
and the increase in wear volume. The morphological
features (Fig. 5) of the fretted zone of Ti6Al4V alloy
conrm the generation of higher quantities of debris and
their entrapment in the fretted zone. The EDX analysis
performed in the regions marked as % of the fretted
zone of CP-Ti and Ti6Al4V alloy reveals their
chemical nature (Fig. 7). For CP-Ti, this region contains
67?83 at-% of Ti, 25?96 at-% of oxygen and 6?21 at-% of
Al (Fig. 7a), which indicates that it is predominantly
oxides of Ti. The presence of Al could have originated
from the alumina ball used as the counterface. For Ti
6Al4V alloy, this region contains 41?53 at-% of Ti,
47?09 at-% of oxygen, 8?93 at-% of Al, 1?44 at-% of V
and 1?01 at-% of Cl (Fig. 7b).
The higher oxygen content indicates that the extent of
oxidation of the fretted zone is relatively higher for Ti
6Al4V alloy compared with that of CP-Ti. The
presence of Al and V, with a corresponding decrease
in Ti, supports the formation of oxides of Al and V in
the fretted zone of Ti6Al4V alloy. The hard and
abrasive nature of the oxides of Al would have increased
the wear rate/wear volume of Ti6Al4V alloy, which is
conrmed by the 3D prole of the fretted zone (Fig. 6).
The higher cathodic shift in FCP of Ti6Al4V alloy
with the onset of fretting, the decrease in tendency of the
alloy to repassivate during fretting and the decrease in
ability of the alloy to revert to the initial steady state
after the fretting motion is ceased assume signicance.
The increase in corrosion susceptibility with the removal
of the passive layer induced by fretting, the poor
tendency for repassivation during fretting and the delay
in reaching the initial steady state potential would
induce leaching of Al and V ions, which could cause
long term health problems like Alzheimer disease and
neuropathy. Osteolysis, adverse tissue reactions, kidney
lesion, cytotoxicity, hypersensitivity and carcinogenesis
have been reported to be associated with V and Al
ions.
5,3335
Vanadium may elicit local or especially
systemic reactions or inhibit cellular proliferation.
Aluminium may be associated with osteomalacia,
pulmonary granulomatosis and neurotoxicity.
34,35
The
accumulation of wear debris may produce an adverse
cellular response, leading to inammation, release of
damaging enzymes, osteolysis, infection, implant loosen-
ing and pain.
36,37
Conclusion
The study on the fretting corrosion behaviour of Ti
6Al4V alloy in Ringers solution and comparison of its
behaviour with that of CP-Ti lead to the following
conclusions.
1. Both CP-Ti and Ti6Al4V alloy exhibit a similar
trend of cathodic shift in FCP with the onset of fretting,
fluctuations in FCP during fretting and anodic shift in
FCP after the fretting motion is ceased. Adhesive galling
is the predominant wear mechanism when they are
fretted against the alumina ball.
2. The fretting corrosion behaviour of Ti6Al4V
alloy differs from that of CP-Ti in terms of: increase in
susceptibility for corrosion upon removal of the passive
oxide layer with the onset of fretting, decrease in
tendency to repassivate during fretting, decrease in
ability to revert to the initial steady state potential after
the fretting motion is ceased, higher amount of
formation and entrapment of debris at the fretted zone
and accumulation of the same at the edges, increased
extent of oxidation leading to the formation of oxides of
7 Analysis (EDX) performed on marked region: region marked as % in Fig. 5c and d of fretted zone of a CP-Ti and b Ti
6Al4V alloy (conditions: as described in Fig. 5)
Sivakumar et al. Corrosion behaviour of Ti6Al4V and CP-Ti in Ringers solution
Tribology 2011 VOL 5 NO 4 163
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Al and V besides Ti and increase in wear volume due to
the abrasive nature of aluminium oxide.
3. The difference in performance of Ti6Al4V alloy
and CP-Ti points out that the choice of materials for
implants that would encounter fretting corrosion should
be made only after a thorough evaluation.
Acknowledgement
The authors express their sincere thanks to Dr S.
Srikanth, Director, National Metallurgical Laboratory,
Jamshedpur, for his constant encouragement and sup-
port and for his permission to publish this paper.
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