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Electrochemical Instrumentation of a Hip Simulator: A New Tool for Assessing

the Role of Corrosion in Metal-On-Metal Hip Joints

Article  in  Proceedings of the Institution of Mechanical Engineers Part H Journal of Engineering in Medicine · November 2010
DOI: 10.1243/09544119JEIM771 · Source: PubMed

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 Proceedings of the Institution of Mechanical
Engineers, Part H: Journal of Engineering in
Medicine
http://pih.sagepub.com/

Electrochemical Instrumentation of a Hip Simulator: A New Tool for Assessing the Role of Corrosion in
Metal-On-Metal Hip Joints
Y Yan, A Neville, D Dowson, S Williams and J Fisher
Proceedings of the Institution of Mechanical Engineers, Part H: Journal of Engineering in Medicine 2010 224: 1267
DOI: 10.1243/09544119JEIM771

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 1267

Electrochemical instrumentation of a hip simulator:

a new tool for assessing the role of corrosion in
metal-on-metal hip joints
Y Yan1,2*, A Neville2, D Dowson2, S Williams3, and J Fisher3
1
Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE), University of Science and
Techology, Beijing, People’s Republic of China
2
Institute of Engineering Thermofluids, Surfaces and Interfaces (iETSI), School of Mechanical Engineering, University of
Leeds, Leeds, UK
3
Institute of Medical and Biological Engineering (iMBE), School of Mechanical Engineering, University of Leeds, Leeds,
UK

The manuscript was received on 10 November 2009 and was accepted after revision for publication on 8 April 2010.

DOI: 10.1243/09544119JEIM771

Abstract: Polyethylene wear debris induced osteolysis has triggered investigations to find
alternative material combinations to the well-established metal-on-polyethylene hip implants.
Owing to some early successful clinical cases, metal-on-metal (MoM) hip replacements have been
attracting more and more interest. There is, however, considerable concern about the propensity of
MoM hip replacements to release metal ions and fine, nanometre-scale metallic wear debris. The
long-term effect from released metal ions and wear particles is still not clear.
To date, all the work on hip simulators focused on assessing mass losses damage has been
referred to as ‘wear’. However, it is known in the field of tribocorrosion that mechanical removal
of the passive layer on Co–Cr alloys can significantly enhance corrosion activity. In total joint
replacements, it is possible that corrosion plays a significant role. However, no one has ever tried
to extract, on a hip simulator, what proportion of the damage is due to mechanical processes and
the corrosion processes. This paper describes the first instrumentation of an integrated hip joint
simulator to provide in-situ electrochemical measurements in real time. The open circuit
potential results are reported to assess the corrosion regime in the absence and presence of
movement at the bearing surfaces. The importance of these measurements is that the real
damage mechanisms can be assessed as a function of the operating cycle.

Keywords: tribology, corrosion, hip implant, hip simulator, tribocorrosion

1 INTRODUCTION One of the major concerns relating to MoM

Total hip replacements, or hip resurfacing forms,
have been shown to be an effective and successful
arthroplasty to relieve pain, restore a range of
motion, and improve walking ability [1–3]. Some
250 000 hip replacements are performed in the US
each year, and about 50 000 in Britain, of which 15–
20 per cent are revision operations [4, 5]. Metal-on-
metal (MoM) hip replacements present a hard-on-
hard bearing interface.
*Corresponding author: School of Mechanical Engineering,
University of Leeds, Woodhouse Lane, Leeds, West Yorkshire
LS2 9JT, UK.
email: Y.Yan@leeds.ac.uk; rockyan@gmail.com
bearings is the release of metal ions and the
potential long-term effects on the patient [6, 7].
There are two sources of metal ions: the corroding
bearing surface, which is activated by the tribological
contact, and/or the dissolution of metal nanoparti-
cles, which are released as debris. Our previous
studies in tribometers have shown that both pro-
cesses are important [8, 9], but it is appreciated that,
in the tribometer, the contact conditions are much
more severe [10], and the kinetics of the corrosion
process are therefore different.
For younger and more active patients, it is possible
that they may require one or more revisions during
their lifetime. MoM hip replacements and hip
resurfacing replacements have become increasingly

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1268 Y Yan, A Neville, D Dowson, S Williams, and J Fisher

popular in recent times owing to theoretical advan- etc.).

tages (less bone resection, less stress shielding, etc.)
   
and indications of promising clinical survival results hmin gu 0:65 w {0:21
~2:75 0 ð1Þ
[6, 7]. However, concern has been expressed about Rx E Rx E 0 Rx2
the potential problems that may arise in later years
owing to the increased amount of metal ions and the [13]
number of very fine metallic wear particles gener-
ated in MoM implants [8, 9]. Although the long-term hmin
l~
0:5 ð2Þ
effect on patients of metal ions and nanometre wear 2
Rah zRa2c
particles is still unknown, it has become a topic of
concern and debate. Adverse tissue reaction, hyper- [13]
sensitivity, and cancer may occur owing to released The lubrication regimes are as follows:
metal ions [8, 9, 11], but long-term clinical evidence
of this for MoM joints has yet to emerge. 1. Boundary lubrication: asperity interactions be-
To date, there has been no attempt to quantify or tween the tribo-couple become more severe, and
understand the rates and mechanisms of corrosion chemical reactions occur under the tribological
in hip prostheses based upon the more realistic conditions to form a protective boundary film
conditions developed in a hip joint simulator. Hip (Fig. 1(a)). In the boundary lubrication regime, l
simulators have been extensively used and refined in is less than 1.
tribological wear studies, and predictions of implant 2. Fluid film lubrication: the lubricant fluid carries
wear have become much more representative of in- the externally applied load entirely, and the two
vivo performance, but still no account of the surfaces are separated by the fluid film (Fig. 1(b)).
corrosion process has been taken. This paper will In the fluid film lubrication regime, l is normally
present results from the first attempt to instrument a greater than 3.
hip simulator to study the interaction between 3. Mixed lubrication: there is some asperity contact,
corrosion and tribology, namely biotribocorrosion, but some hydrodynamic (fluid film) providing
occurring at the bearing interface. It demonstrates partial separation. The load is shared between the
how this newly instrumented cell offers opportu- contacting asperities and the fluid film (Fig. 1(c)).
nities to understand aspects of degradation not In this lubrication regime, the l value is normally
previously accessible through conventional gravi- between 1 and 3.
metric analysis
The ProSim hip simulator used in the experiments
conformed to the ISO 14242-1 standard. The acet-
2 EXPERIMENTATION AND MATERIALS

The loading cycles and motion used in hip simula-

tors are normally chosen to represent steady walking
conditions [12]. For all tests reported in this paper,
the nominal diameters of the femoral heads were
36 mm, and the diametrical clearances (the diame-
trical difference between the cup and the femoral
head) were in the range of 100–128 m. All cups and
heads of the tested hip implants were made from
high carbon (0.2 per cent C) wrought CoCrMo alloys.
There are three lubrication regimes depending on
the load, the relative velocity, the viscosity of the
lubricant, the surface roughness, etc. [13]. A para-
meter, the lambda ratio, l, is used to determine in
which lubrication regime a tribological system
operates (equations (1) and (2)). It has been used
widely in bearing design. The lambda ratio l is also
called the film thickness ratio. It is related to the Fig. 1 Lubrication regimes: (a) boundary lubrication,
surface roughness, properties of the lubricants (b) full fluid film lubrication, and (c) mixed
(viscosity), and operating conditions (load, velocity, lubrication

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 Electrochemical instrumentation of a hip simulator 1269

abular cup with a wire attached was mounted in
bone cement at 45u to the horizontal plane and
positioned anatomically on the top of the head
(Fig. 2). The cup acted as the working electrode (WE)
in the three-electrode system. A silver/silver chloride
reference electrode (RE) was attached on the wall of
the cup holder with a platinum wire as a counter
electrode (CE). The hip simulator had flexion–
extension of 215u–30u and internal–external rotation
of ¡10u. A twin peak loading cycle was applied
vertically to the head with a peak load of 3 kN and a
swing phase load of 280 N (Fig. 3). Tests were carried
out in 25% (v/v) bovine serum supplemented with
0.1% (w/v) sodium azide to retard bacterial growth.
Each test was conducted for 450 000 cycles
(125 hours). The frequency of the motion was
controlled at 1 Hz. The open circuit potential (OCP)
was monitored during tests.
The ball on flat reciprocating tribometer has been
discussed in detail elsewhere [14, 15], but the key
parameters were:
(a) load/stress starting contact 5 80 N/112 MPa
(b) stroke length 5 20 min
(c) frequency 5 1 Hz.
The lubrication regimes of the simulator and the
tribometer are discussed later in the paper.
At the OCP, the anodic reaction rate equals the
cathodic reaction rate, and so there is no net current
flow to or from the working electrode. It represents a

Fig. 2 The ProSim hip simulator used for the tests in this study: the electrodes were contained
within serum, and the electrochemical connection was made to the acetabular cup

Fig. 3 Applied load and movement cycle (internal–external rotation of ¡10u and flexion–
extension rotation of 215–30u) on the simulator

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1270 Y Yan, A Neville, D Dowson, S Williams, and J Fisher
type of dynamic equilibrium where there is no
external polarization of the electrode [16]. The value
of the OCP is often used to give a semi-quantitative
indication of the corrosion regime (active or passive)
in which a material resides. It can provide a useful
way to differentiate conditions of active corrosion
(more negative) from passive conditions (more
noble). In this study, measurement of the OCP was
used to assess (a) how the action of sliding in the
MoM hip joint affects the passivity of the system and
(b) if depassivated during sliding, how the material
‘recovers’ once the sliding wear ceases.
3 RESULTS AND DISCUSSION
The OCP was monitored prior to the movement,
after the cup and head were in contact, during the
tests, and then for 20 min after the cyclic motion and
loading were stopped. As soon as the motion started,
the OCP shifted in the more negative (active)
direction (Fig. 4). Similar trends of potential shifts
have been observed in previous studies using
reciprocating and rotating/reciprocating tribometers
(Fig. 4(c)) [14, 15].
Metallic materials used in hip implants are highly
corrosion-resistant and fall in the category of
‘passive’ materials, possessing an extremely tena-
cious and thin (. 50 nm) passive layer rich in Cr.
Ions are still produced in such hip bearing systems,
one route being through the mechanical damage of
this passive layer during sliding and, hence, the
removal of the protective barrier. Removal of the
passive film induces high corrosion rates, and the
overall damage and loss of material from the bearing
components can be high and comprise processes of
mechanical wear, electrochemical corrosion, and
interactions between these two. The change of the
potential value indicates damage of the passive film
on the hip implant such that part of the surface is
depassivated. Depassivation refers to the corrosion
state that results when the passive film can no longer
provide an effective barrier to charge transfer.
Because of the dynamic nature of the hip
simulator movement, the severity of asperity inter-
action in the mixed lubrication regime fluctuates
such that the bare surface of the material is
periodically exposed to the local environment and
corrodes again. This involves the release of metal
ions, and then, as the severity of local contact is
relieved, a new passive film will be formed (repassi-
vation). Comparing Figs 4(b) and 4(c), the depassi-
vation rate (the decrease rate of the OCP value) for
the CoCrMo components in the hip simulator was
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much lower than in the reciprocating tribometer
tests. It took longer for the material to reach a
dynamic equilibrium in the hip simulator, typically
in excess of 4000 s. This is owing to the less severe
tribological environment in the hip simulator, which
is discussed later. Following the kinetics of potential
upon loading and unloading offers great potential to
understand how the passive film responds as a
function of the loading and movement cycle.
Figure 5 is a schematic Evans’ diagram of the
anodic (metal-to-metal ion, i.e. Co R Co2+ + 2e) and
cathodic (oxygen reduction/hydrogen evolution)
processes that make up the electrochemical (corro-
sion) reactions. When the components were static,
OCP1 was the equilibrium point where the anodic
reaction equalled the cathodic reaction. Owing to
tribological contact, the anodic processes are depo-
larized (speed up), and the change in rate dominates
the Evans diagram. This change of rate results in a
lower (more active) OCP value (OCP2) being
obtained. In addition, a higher current value (i2)
corresponding to OCP2 indicates a greater material
loss due to electrochemical processes.
In the cyclic nature of the movement, different
areas are depassivated and repassivated, and this
leads to a dynamic equilibrium being achieved.
Compared with the measurements on the recipro-
cating tribometer, the hip simulator, which has
multidirectional movement and dynamic loading,
showed a lower potential shift. This can be rationa-
lized by considering the lubrication regimes in both
the simulator and the tribometer. From an assess-
ment of the film thickness ratio, it is clear that the
conditions in the tribometer are in the boundary
lubrication regime, as the l value is , 1. In the
simulator, the l value is greater, indicative of less
asperity contact and more areas of thin-film lubrica-
tion (here, l is approximated to be 1.69). Less metal-
to-metal asperity contact clearly gives less shift in
OCP, which is aligned with the lower amount of
charge transfer at the contact. There is a great
potential for in-situ, real-time electrochemical mea-
surements in hip simulators to assist in under-
standing the interfacial processes at MoM bearing
surfaces.
An ennoblement of potential was observed after
about 100 000 cycles, as shown in Fig. 4(a). It is
unlikely that, at that time, there was any significant
change in the cathodic processes at the interface;
changes in the cathodic processes can also lead to
ennoblement (Fig. 5). It is therefore more likely that
the anodic reaction rate was altered through the
formation of a surface film; a positive shift repre-
JEIM771
 Electrochemical instrumentation of a hip simulator 1271

Fig. 4 The OCP as a function of time for materials with 25% serum: (a) in the hip simulator for
450 000 cycles, (b) the initial 6000 cycles as in (a), and (c) the initial 800 cycles in a pin-on-
plate reciprocating tribometer

sents a slowing of the anodic reaction rate. Hence,
reduced ion transport occurred at the bearing inter-
face.
It should also be noticed that there is a transient
period of a potential dip and ennoblement at the
very beginning of the tests (around 10 000 cycles)
(Fig. 4 (a)). From previous tribometer work, we
postulate that this is related to the chemical change
at the interface of the contact. The native passive
films (oxides) were rubbed off in the first few cycles,

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1272 Y Yan, A Neville, D Dowson, S Williams, and J Fisher
Fig. 5 An Evan diagram illustrating how OCP changes
OWING to enhanced anodic reaction
and a more complex tribofilm of organic species,
together with oxides and hydroxides of cobalt and
chromium, was formed.
Mapping such changes in ion release from the
bearing surfaces in situ and correlating this to
analysis of surface tribofilms, which will be the
subject of future papers, are extremely powerful in
understanding rates and mechanisms of ion release
and also for looking towards means of retarding ion
release.
4 CONCLUSIONS AND LOOKING FORWARD
The first attempt to perform in-situ electrochemical
measurements on hip joint simulators is reported in
this paper. It provides a powerful tool to facilitate
detailed live measurements of charge transfer rates
to enhance the understanding of the reactions at
load-bearing surfaces of hip implants. This level of
information is not currently accessible from con-
ventional gravimetric measurements. Laboratory
tribometers and hip prosthesis simulators show
comparable trends in terms of electrochemical
behaviour. However, owing to reduced severity of
contact in the simulator conditions (boundary
lubrication to mixed lubrication), the extent of
mechanical damage is less severe, and this is clearly
recognizable from the reported measurements.
Smaller potential shifts are recorded for hip simula-
tors. Shifts in potential during operation are likely to
be a result of tribofilms forming on the bearing
surface, which, from previous work on tribometers
and explants, consist of organometallic species and
can offer effective resistance to further corrosion.
There has been a long history of the development
of wear measurements on hip simulators. In this
study, the integrated hip simulator can also provide
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the possibility to quantify the damage caused by
corrosion and corrosion-related reactions. The cor-
rosion rate (ion release rate) can also be related to
loading conditions (edge loading, microseparation,
etc.). The cathodic protection (CP) method can be
used to isolate pure mechanical wear from the total
mass loss. The mechanisms of metallic-ion release in
the complex biotribocorrosion systems can then be
assessed in detail. The ultimate goal for the whole
study is to decrease the corrosion process and to
reduce the amount of released metallic ions and
debris. From bench wear testers, some interesting
results were obtained, and, using the more realistic
hip simulator, assessments will be made to prove the
concept. By integrating the hip simulator, it is also
possible to study further the lubrication regimes for
hip implants during operation conditions.
ACKNOWLEDGEMENTS
This work is supported by the ARC, UK. The hip
components were supplied by De Puy International.
F Authors 2010
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