ARTICLE IN PRESS

Tribology International 43 (2010) 12181227

Contents lists available at ScienceDirect

Tribology International
journal homepage: www.elsevier.com/locate/triboint

Interpretation of electrochemical measurements made during micro-scale

abrasion-corrosion
R.J.K. Wood a,, D. Sun a,b, M.R. Thakarea,c, A. de Frutos Rozas a,d, J.A. Wharton a
a
National Centre for Advanced Tribology at Southampton, School of Engineering Sciences, University of Southampton, Higheld, Southampton SO17 1BJ, UK
b
NIBEC, University of Ulster, Jordanstown Campus, Co. Antrim, BT37 0QB Northern Ireland, UK
c
Schlumberger Oileld UK Plc, Stonehouse Technology Centre, Brunel Way, Stroudwater Business Park, Stonehouse, Glos GL10 3SX, UK
d
Department of Corrosion and Protection, National Centre for Metallurgical Research, CENIM-CSIC, Av. Gregorio del Amo 8, E-28040 Madrid, Spain

a r t i c l e in f o a b s t r a c t

Article history: This paper brings together and analyzes recent work based on the interpretation of the electrochemical
Received 28 July 2009 measurements made on a modied micro-abrasion-corrosion tester used in several research
Received in revised form programmes. These programmes investigated the role of abradant size, test solution pH in abrasion-
21 December 2009
corrosion of biomaterials, the abrasion-corrosion performance of sintered and thermally sprayed
Accepted 13 January 2010
Available online 2 February 2010
tungsten carbide surfaces under downhole drilling environments and the abrasion-corrosion of UNS
S32205 duplex stainless steel. Various abrasion tests were conducted under two-body grooving, three-
Keywords: body rolling and mixed grooving-rolling abrasion conditions, with and without abrasives, on cast F75
Tribocorrosion cobaltchromiummolybdenum (CoCrMo) alloy in simulated body uids, 2205 in chloride containing
Microabrasion
solutions as well as sprayed and sintered tungsten carbide surfaces in simulated downhole uids.
Electrochemical
Pre- and post-test inspections based on optical and scanning electron microscopy analysis are used to
Synergy
help interpret the electrochemical response and current noise measurements made in situ during
micro-abrasion-corrosion tests. The complex wear and corrosion mechanisms and their dependence on
the microstructure and surface composition as a function of the pH, abrasive concentration, size and
type are detailed and linked to the electrochemical signals. The electrochemical versus mechanical
processes are plotted for different test parameters and this new approach is used to interpret tribo-
corrosion test data to give greater insights into different tribo-corrosion systems. Thus new approaches
to interpreting in-situ electrochemical responses to surfaces under different abrasive wear rates,
different abrasives and liquid environments (pH and NaCl levels) are made. This representation is
directly related to the mechano-electrochemical processes on the surface and avoids quantication of
numerous synergistic, antagonistic and additive terms associated with repeat experiments.
& 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Many corrosion resistant metallic materials rely on a surface
oxide lm to provide protection against corrosion. However,
under an externally applied stress or during wear, this passive
oxide lm may become cracked and/or removed, exposing the
substrate to a corrosive environment and leading to enhanced
surface degradation. Therefore, it is important to be able to select
or design surfaces that have the correct balance between the
ability to repassivate in the service environment while not being
too reactive when corroding or in regimes where repassivation is
not complete (i.e. in wearing contacts). This is of particular
concern for many engineering and bioengineering applications
that are subjected to wear and corrosion such as pumps and
 Corresponding author. Tel.: + 44 2380 594881.
E-mail addresses: rjw3@soton.ac.uk, R.Wood@solon.ac.uk (R.J.K. Wood).
valves in the process, oil and gas and marine industries, as well as
metallic surgical implants used to replace human joints [1,2].
Materials selected primarily on their corrosion resistance under
benign conditions can suffer highly interactive processes when
subjected to wear and corrosion together. These interactions lead
to accelerated wall wastage and ion release rates which can
compromise component life and also induce adverse reactions if
released within the body [3].
Previous work at Southampton has investigated the interaction
between abrasion and corrosion on various stainless and super
duplex steels [4]. Both UNS S31603 and S32760 stainless steels
produced interactions such that the abrasioncorrosion levels
were below the pure abrasion levels under two-body grooving
abrasion conditions while the reverse was true for S30403. These
large negative interactions were due to the differences in
repassivation kinetics and/or composition of the passive lms
reducing the overall level of two-body abrasion [4]. However, all
three stainless steel types under three-body rolling abrasion

0301-679X/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2010.01.004
 ARTICLE IN PRESS
R.J.K. Wood et al. / Tribology International 43 (2010) 12181227
showed improved reproducibility with increasing abrasive vo-
lume fraction with abrasioncorrosion levels greater than pure
abrasion levels by 18%. Although this work did not utilize in-situ
electrochemical measurement of tribocorrosion currents induced
during abrasioncorrosion various studies have measured cur-
rents during abrasioncorrosion tests of biomaterials and down-
hole hardfacing materials as well as numerous engineering
coatings [57]. These individually show different trends and
sensitivity to test environment and conditions. Therefore the aim
of this paper is to reanalyze and investigate the wear and
electrochemical interactions to allow more robust selection of
surfaces for abrasioncorrosion resistant applications. The paper
also presents new data for UNS S32205 duplex stainless steel
which is included as it is commonly found in marine applications
or other high chlorine conditions due to its superior corrosion
performance. The other surfaces investigated were a sintered
WC5.7Co0.3Cr hard metal, a high velocity oxy fuel (HVOF)
sprayed WC10Co4Cr coating and a cast F-75 CoCrMo bioengi-
neering alloy. Tungsten carbide (WC)-based hardmetals and
coatings, CoCrMo based alloys and stainless steels are materials
which readily form a passive oxide lm and are therefore likely to
have interesting wear-corrosion properties.
An HVOF WCCo coating was chosen as this type of coating is
increasingly being used as a chromium coating replacement.
However, HVOF WCCo coatings are microstructurally complex
potentially leading to internal micro-galvanic corrosion activity
and thus destablising the overall coating surface integrity. This
has been seen in the corrosion and corrosionwear behaviour of
HVOF sprayed WC cermet coatings with metallic binders of Co,
CoCr, CrCNi and Ni, in strong acidic environments by Cho et al.
[8]. Considerable micro-galvanic corrosion occurred between the
WC particles and the binder, and uniform corrosion occurred in
the binder materials of WCCo and WCNi. These coatings are
often bench marked against sintered hardmetal of similar
composition therefore this paper has included analysis of a
sintered WCCoCr material to allow comparisons. The WC-based
hardmetals and coatings are commonly utilized for their superior
wear resistance in downhole drilling components. Downhole
environments subject these materials to harsh tribological
conditions, such as two- and three-body abrasion in the presence
of alkaline drilling uids.
Recently, micro-abrasion tests coupled with an electrochemi-
cal cell, have been deployed to study the abrasioncorrosion
behaviour of these engineering materials under conditions where
corrosive electrolyte and third body abrasives co-exist [911]. The
microscale abrasioncorrosion performance of two sintered
hardmetals, WC6Co and WC11Ni, and two WC10Co4Cr
sprayed coatings using both NaOH (pH 11) and neutral SiC
aqueous slurries. Contrary to expectations, micro-abrasion under
alkaline conditions generally resulted in lower wear rates
producing a negative 818% abrasioncorrosion interaction, with
the exception of the sintered WC11Ni [9,10].
The CoCrMo alloys, on the other hand, are commonly used in
metal-on-metal (MoM) hip replacement surgery and are exposed
to oxygenated and chloride containing body uids and tissues.
The relative motion of femoral ball and cup will generate wear
debris, some of which can act as third body abrasives yielding
further abrasive wear of the bearing surfaces. The depassivation of
the surfaces does promote metal ion (cobalt and chromium)
release both have biocapatability issues and can iname the
tissues in the joint area which may subsequently cause pain and
hypersensitivity for patients [1214]. Retrieved metal-on-metal
hip replacements have revealed that two and three-body abrasive
are dominant wear mechanisms. Therefore the need to under-
stand the tribocorrosion performance of these surfaces is critical
to the continued use of the MoM joint replacements.
1219
Micro-abrasioncorrosion testing has also been conducted in
0.9% NaCl, phosphate buffered saline solution, 25% and 50%
bovine serum solutions with 0 or 1 g cm  3 SiC abradant at 37 1C.
The results show the presence of proteinaceous material
increased the total specic wear rate (SWR). Conversely, electro-
chemical noise measurements indicated that the average anodic
current levels were appreciably lower for the proteinaceous
solutions when compared with the inorganic solutions [11].
Therefore, this paper will assess the wearcorrosion perfor-
mance of four metallic surfaces with different repassivation
characteristics to see if the trends between mechanical and
electrochemical responses are affected by repassivation charac-
teristics.
2. Experimental
The test materials studied include a cast cobalt-based
bioengineering alloy (ASTM F75 CoCrMo2527% Cr, 57% Mo
and the balance Co) used in metal-on-metal replacement joints; a
sintered hardmetal (WC-CoCr); a thermally sprayed hard coating
(WC-CoCr); as well as corrosion resistant alloy. The corrosion
resistant alloy chosen was UNS S32205 duplex stainless steel as
this has superior corrosion resistance, particularly against
seawater, compared with Grade 316. It has excellent resistance
to localized corrosion including intergranular, pitting and crevice
corrosion; the critical pitting temperature of 2205 is generally at
least 35 1C.
Fig. 1(a) shows that sintered WC-based hardmetals have a
typical skeletal carbide structure. The size of the carbides was
23 mm. Fig. 1(b) shows the SEM (backscattered electron image)
image of a polished WC-10Co4Cr surface. The darker regions
represent the heavier elements, such as tungsten in the
composition and the lighter regions represent the relatively
lighter elements, such as cobalt, chromium and nickel. The
micrography shows an inhomogeneous distribution of carbide
rich and binder rich areas along with the presence of some voids
and cracks formed on the surface during the cooling of the
coating. Fig. 1(c) shows that cast CoCrMo (consists of blocky-
shape M23C6 primary carbides (1030 mm in size, where M is Cr,
Mo and Co [15]) incorporated in the cobalt rich matrix. The
carbides are standing proud of the Co-matrix (  200 nm higher
according to atomic force microscopy analysis). It is believed that
these hard asperities can protect the softer matrix and reduce
wear in the event of lubrication lm starvation [16]. Fig. 1(d)
shows the 2205 stainless steel microstructure after electrolytic
etching in 40% KOH at 1.5 V for 1 min. The elemental composition
of the 2205 duplex stainless steel was Fe, o0.03% C, 2123% Cr,
4.56.5% Ni, 2.53.5% Mo, 0.82.0% N, o2% Mn, o1% Si, o0.03%
P and o0.02% S. The lighter areas correspond to d ferrite and
darker regions are g austenite. The ferrite and austenite contents
are nearly 50%, with the austenite evenly distributed within the
ferrite. Additionally, some black spots can be observed, which are
probably sites of MnS inclusions that probably have been
dissolved during the etching procedure.
The hardness values of each material are shown in Table 1
along with the hardness of the counter face (a zirconia ball) and
the silicon carbide (SiC) and alumina (Al2O3) abradants. The
abradants were chosen either to mimic the carbide hardness of
the CoCrMo or to conform to previous test conditions where
highly reproducible results were obtained with effective particle
entrainment into the contact. Abradant concentrations were
chosen to control the abrasion mechanism from two (grooving)
to three body (rolling) with increasing concentrations.
A modied Phoenix Tribology TE/66 microabrasion tester
incorporating a liquid tank and a 3-electrode electrochemical cell
 ARTICLE IN PRESS
1220 R.J.K. Wood et al. / Tribology International 43 (2010) 12181227

Fig. 1. SEM analysis showing the microstructure of (a) sintered WC-5.7Co0.3Cr hard metal, (b) sprayed WC-10Co4Cr coating, (c) cast F-75 CoCrMo alloy and
(d) UNS S32205 duplex stainless steel.

Table 1 In situ electrochemical current-noise was measured under

Vickers microindentation hardness (2.94 N) of the counterface, abrasive and an applied potential (the open circuit potential of the testing
materials used in this study in GPa.
metal) using a Gamry potentiostat and ESA 400 software. This
Zirconia SiC Al2O3 Sintered Sprayed Cast 2205 follows other workers in the eld of tribocorrosion [17]. The
ball abrasive abrasive WC- WC- CoCrMo duplex electrochemical current-noise sampling rate was 2 Hz. Each test
counterface 4.5 mm 1.7 mm 5.7Co 10Co stainless has been repeated at least twice to gauge repeatability. The size of
0.3Cr 4Cr steel the wear scar can be measured in situ using a calibrated eye piece
13.0 2126 1820 17.7 11.1 3.3 2.9
on the microabrasion rig and wear volume and wear rate can be
calculated using Eq. (1) [18]:

pb4
V for b{R 1
64R
Table 2
Test conditions for sintered WC-5.7Co0.3Cr and sprayed WC-10Co4Cr coating. where V is the wear volume (m3), b the diameter of wear scar (m)
and R the radius of the ball (m). Assuming the specimen is
Load 0.2 N
homogeneous (i.e. the wear rate is constant such that the wear
Abrasive slurry 4.5 mm SiC suspended in solutions of NaOH+ NaNO3
(pH 9, 11, 13) or NaNO3 of pH 7 volume is proportional to the load and sliding distance), the
Slurry volume 0.166 specic wear rate SWR (m3 N  1 m  1) can be calculated by the
concentration Archard equation [19,20] (Eq. (2)):
Sliding distance/speed 30 m/0.05 m s  1
Exposure time Freshly polished or exposed (in pH 7 and 11 V
SWR 2
solutions) for 168 h WL
where SWR (mm3 N  1 m  1) is a dimensional wear coefcient and
Table 3
represents the volume of material removed by wear per unit
Test conditions for cast CoCrMo and 2205 duplex stainless steel. distance (L in m) slid per unit normal load (W in N) on the contact.
The average current was calculated from the current versus
Load 0.25 N time curve using Eq. (3):
Abrasive slurry 4.5 mm SiC or 1.7 mm Al2O3 suspended in 0.9%
Rt
NaCl or 3.5% NaCl I dt
Slurry volume 0.006, 0.072, 0.030, 0.12 (0.238 for CoCrMo Iave 0 3
concentration at pH 7 only)
t
Sliding distance/speed 38 m/0.05 m s  1 where I is the current and t the duration of the test. It is
Exposure time Immerse in testing solution for 30 min prior to
proportional to the total charge transfer that occurs during the
tests
abrasion-corrosion process and can be correlated to the material
loss, Wm, due to the electrochemical dissolution using Faradays
was used, the detailed structure of the rig can be found elsewhere law, see Eq. (4):
[11]. All samples were machined to a dimension of 20 mm  10 Mr Q
mm  3 mm and were ground/polished down to 1 mm diamond Wm 4
zF
paste. A pre-conditioned zirconia ball was rotated against the
sample under a specied load and in the presence of abrasive where Mr is the molar mass of the material, z the number of
slurry. The detailed test conditions for each material can be found electrons transferred in the reaction, F the Faradays constant and
in Tables 2 and 3, respectively. Q the total charge given by Eq. (5):
The abrasives used for the micro-abrasion corrosion tests are
4.5 mm SiC (Grade F1200, Washington Mills Ltd., Manchester, UK) Z
and/or 1.7 mm Al2O3 (Logitech Ltd., UK). Their microstructures are Q I dt 5
shown in Fig. 2(a) and (b), respectively.

R.J.K. Wood et al. / Tribology International 43 (2010) 12181227
Fig. 2. (a) 4.3 SiC mm and (b) 1.67 mm Al2O3 abrasives used in this study.
WC-5.7Co-0.3Cr pH 7
WC-5.7Co-0.3Cr pH 9
100
90
80
70
60
Current /A
50
40
30
20
10
0
0 200
-10
Fig. 3. Current-noise response for sintered WC-5.7Co0.3C under different test conditions.
3. Results and discussion
Fig. 3 shows the current-noise (It) response for fresh and
exposed (-exp) sintered WC-5.7Co0.3C samples obtained during
micro-abrasion tests using alkaline (pH 9, pH 11 and pH 13) and
neutral (pH 7) abrasive slurries. The current gradually increased
throughout the wear test duration associated with the increase in
the wear scar area with time. The current levels and the curve
shapes observed for pH 7, pH 9, pH 11 and pH 11-exp samples are
generally similar (less than 30 mA). However, higher current
values are observed for pH 7-exp (80 mA) and pH 13 (90 mA)
samples. The shape of the It curves for pH 7-exp and pH 13
samples are distinctly different from the conditions. A steep rise
in current is observed between 100 and 200 s after abrasion
began, particularly for the pH 7-exp sample. This can be explained
by the Pourbaix diagram of Co (Fig. 4), where the Co binder is
more prone to dissolution at pH 7 and pH 13 [21]. It is also likely
to be due to the increased electrochemical dissolution of the
binder phase due to micro-galvanic coupling between the nascent
wear scar and the unworn area of the passive surrounding (due to
exposure). The other distinctive feature of the pH 7-exp and pH 13
ARTICLE IN PRESS
1221
WC-5.7Co-0.3Cr pH 11 WC-5.7Co-0.3Cr pH 7-exp
WC-5.7Co-0.3Cr pH 11-exp WC-5.7Co-0.3Cr pH 13
Depletion of binder
400 600 800 1000 1200 1400 1600
Time / s
curves is the reduction in current approximately half way through
the test. This is thought to be due to binder phase depletion
between the carbides and/or local pH variation within the cavity
created by binder depletion between carbides. The partial decay
of currents (i.e. the currents do not reduce to original pre-test
levels) seen in Fig. 3 after the ball has stopped rotating suggests
that the wear scar did not readily repassivate when in contact
with neutral and alkaline slurries due to the depletion of the
binder phase and the local environment within cavities between
carbides. The partial decay effect is seen for all pH conditions
tested but is not seen on the other materials tested in this work as
they have dispersed carbides which do not suffer such localized
corrosion.
Fig. 5 shows a plot of the average current, Iave, values measured
during micro-abrasion against the SWR sintered WC-5.7Co0.3Cr.
The SWR is predominately inuenced by mechanical wear
processes but will contain a small component of material
removed by corrosion. No obvious relationship between SWR
and Iave is seen under neutral and weak alkaline conditions.
Overall, mechanical wear processes occurred by fragmentation
and loosening of carbide grains but only the top surface carbides
 ARTICLE IN PRESS
1222 R.J.K. Wood et al. / Tribology International 43 (2010) 12181227

To study the wear mechanisms occurring on the sintered WC-

5.7Co0.3C samples, typical SEM images of worn sample wear
scars generated in neutral (pH 7) and alkaline (pH 11 and pH 13)
slurries are presented in Fig. 6. For consistency, all images were
obtained from the wear scars centres for all samples. The worn
surfaces of the sintered samples appeared to be similar for other
test conditions and are devoid of any binder, compared with the
unworn surface (Fig. 6a). The carbide grains within the wear scar
appear to have suffered from repeated fragmentation and
fracture. The size of the fragmented carbides in neutral and weak
alkaline conditions (pH 7, pH 9 and pH 11) is similar, which
indicates that the rate of binder dissolution suffered by
these samples is also similar. However, pH 13 sample (Fig. 6d)
shows severely fragmented carbide grains on the surface which is
likely to be caused by excessive binder depletion during micro-
abrasion. Hence, for this surface there is no obvious relationship
between average current and SWR as the wear mechanism is not
affected by the subtle variation in current associated with
different levels of passivation of the binder phase between
carbides on the surface. Only under pH 13 where the binder
phase is actively corroding does the surface layer of carbides
become undermined by excessive binder removal and fractures
causing an increase in SWR.
Fig. 7 shows the electrochemical current noise response for the
WC-10Co4Cr coating during micro-abrasion tests for different
pH. The It curves show a sharp rise in the current immediately
after the abrasion test begins. This sharp rise in current is
observed due to the removal/damage of the passive Co(OH)2 lm
Fig. 4. Pourbaix diagram for cobalt [21]. on the binder rich areas. After the initial rise in the current it
attains a relatively steady value. The current levels do not change
substantially for the remaining duration of the micro-abrasion
70 test despite the increase in the wear scar area. The uctuation in
the current is due to the spontaneous repassivation within the
pH 7-exp
pH 7 wear scar and subsequent depassivation due to the action of
60
pH 9 abrasive particles. At the end of each test the current levels
pH 11 sharply drop to similar values as seen before abrasion. This is due
50 pH 11-exp
to the repassivation of the wear scar after the ball rotation
Average current / A

pH 13
40
30
20
10
0 wear scar.
0 2x10-13 4x10-13
SWR / m3 N-1 m-1
Fig. 5. Average current and SWR relationship for sintered WC-5.7Co0.3Cr.
were damaged determined by SEM and focused ion beam analysis
(results not shown here). This is probably due to the skeletal
structure of the carbides supporting the abrasive loading on the
top carbides while carbide fracture occurs via individual
transgranular cracking with carbide boundaries inhibiting
intergranular fracture. A maximum current is observed for the
pH 13 samples which also resulted in the highest SWR, possibly
due to the excessive rate of binder depletion observed under pH
13. The increase in wear rate is likely to be due to excessive binder
depletion around the top carbides that enhances unsupported
carbide fracture and pull-out. The results can be correlated with
the wear scar morphology as shown in Fig. 6.
stopped. This further corroborates that binder-rich areas within
the wear scar readily passivate in the absence of abrasion. This is
in contrast to the sintered hardmetal which has a small surface
area of binder phase exposed compared with the sprayed coating
with far grater exposed binder phase and does not have a skeletal
carbide matrix and therefore does not readily form cavities
between carbides. A similar current-noise behaviour was
observed during the reciprocating-sliding wear of passive metals
(316 stainless steel, chromium and nickel) by Mischler et al. [22].
It was reported that the variation of the measured anodic current
was the measure of the electrochemical metal removal rate in the
6x10-13 Fig. 7 shows that the maximum current levels observed for pH
7, pH 9, pH 11 and pH 11-exp are similar (less than 5 mA).
However, higher current values are observed for pH 7-exp
samples (10 mA) and pH 13 samples (25 mA). Interestingly, the
current observed for pH7-exp samples was higher than for the pH
7 samples. This is likely to be due to the microgalvanic coupling
between the nascent surface in the wear scar and the surrounding
area of the pH 7-exp sample leading to increased electrochemical
dissolution. The wear scar is expected to be more active as
compared with the relatively passive surrounding (due to
exposure) leading to higher corrosion within the wear scar.
Micro-galvanic coupling between the active wear scar and the
relatively passive unworn areas is likely to occur for all samples.
The high current values observed for pH 13 samples are expected
due to the greater tendency of W, Co and Cr to corrode at pH 13.
Fig. 8 shows the average current measured during microabrasion
against SWR for the fresh and exposed WC-10Co4Cr coatings
 ARTICLE IN PRESS
R.J.K. Wood et al. / Tribology International 43 (2010) 12181227 1223

Fig. 6. SEM micrographs of wear scars on the sintered WC-5.7Co0.3 samples (a) unworn surface and (b) worn in pH 7, (c) worn in pH 11 and (d) worn in pH 13 conditions.

WC-10Co-4Cr pH 7-exp WC-10Co-4Cr pH 13 WC-10Co-4Cr pH 11

WC-10Co-4Cr pH 7 WC-10Co-4Cr pH 9 WC-10Co-4Cr pH 11-exp

30

25

20
Current / A

15

10

0
0 200 400 600 800 1000 1200 1400 1600

-5
Time / s

Fig. 7. Current-noise response of sprayed WC-10Co4Cr coating under different test conditions.

abraded using neutral and alkaline slurries. No obvious relationship
exists between increases in the average current and the SWR under
neutral and wear alkaline conditions. However, the lowest current
and SWR are observed for pH 11 and pH 11-exp samples while the
highest current and SWR observed for the pH 13 sample. As shown in
Fig. 4, at pH 11 Co is expected to form a passive oxide lm Co(OH)2,
which is likely to lower the rate of binder removal. It is also seen from
Fig. 8 that the use of pH 9 and 11 has resulted in a lower SWR as
compared with pH 7. This indicates that pH 7 should not be
considered as a corrosion-free condition. Therefore, as with the WC-
5.7Co0.3C samples, the binder is passivated under the pH 911
range while at pH 7-exp and 13 the binder is actively corroding which
exposes the surface carbides and enhances carbide release and
thereby the SWR levels.
SEM micrographs of worn samples were studied to determine
the wear mechanisms that occurred on the sprayed coatings.
 ARTICLE IN PRESS
1224 R.J.K. Wood et al. / Tribology International 43 (2010) 12181227
Fig. 9 compares the unworn surface of the WC-10Co4Cr coating
to the wear scars on pH 11 sample. Due to the non-uniform
microstructure of the coating the number of carbides exposed in
each case is expected to differ. In general for all samples, the SEM
micrographs reveal that wear has occurred by preferential
removal of binder around the carbide grains, leading to the
cracking and subsequent removal of the carbide grains. The
preferential binder removal leads to the formation of a moat-like
feature around the carbide grains. This feature is observed on all
worn surfaces and appears to be principally in the direction of the
motion of abrasive slurry and is formed due to the preferential
depletion of the binder phase around the carbide grains.
Microabrasion-corrosion of cast CoCrMo has been carried out
using different saline based abrasive slurries at various concen-
trations of SiC and Al2O3 abrasives (0.238, 0.120, 0.072, 0.030 and
0.006 vol%). Fig. 10 shows the typical current-noise curves seen
for cast CoCrMo with 0.072 vol% SiC and Al2O3 abrasive slurries.
The current-noise level under SiC test conditions is generally
higher than that for the Al2O3 test conditions. From the start of
the test, the current shows a sharp increase which corresponds to
the rupture of the surface oxide lm. The current is then
maintained at a relatively constant level throughout the test
due to the stable competition between the depassivation/
repassivation processes. In contrast to WC-5.7Co0.3Cr, the
current after the CoCrMo abrasion recovers to the pre-abrasion
30
pH 7-exp
25 pH 7
pH 9
pH 11
pH 11-exp
Average current / A
20 pH 13
15
10
5
0 -5
0 5.0x10-13 10-12 1.5x10-12 2.0x10-12 2.5x10-12
SWR / m3 N-1 m-1
Fig. 8. Average current and SWR relationship for sprayed WC-10Co4Cr coating.
Fig. 9. SEM micrographs of wear scars on sprayed coatings (a) unworn surface and (b) worn in pH 11 condition.
level indicating the repassivation has effectively inhibited the
wear-induced corrosion current.
Fig. 11 shows the interdependence of the SWR and the average
current for cast CoCrMo abraded in 0.9% NaCl based slurries. For
both SiC and Al2O3, the average current decreases as the SWR
decreases. A linear correlation was found for data sets of both
abrasives (R2 values greater than 0.93). The slope of the linear t
for Al2O3 data (2.1  1013 mA m  2 N  1) is approximately twice
that for SiC (0.88  1013 mA m  2 N  1), indicating that for the same
volume of alloy removed, the smaller sized abrasives could
generate a greater electrochemical response (current) under the
abrasion-corrosion. This could be attributed to the fact that the
time for repassivation between particle impacts was reduced
signicantly by a reduction in particle size [23]. The above
statement is supported by the SEM investigation, see Fig. 12,
where the wear scars generated by Al2O3 contained more
numerous and ner indents (for 0.238 vol%) or grooves (for
0.072 vol%).
Fig. 13 shows the current-noise curves for the 2205 duplex
stainless steel at different SiC volume concentrations in 3.5% NaCl
solution. A sharp increase in the current is noticed when the
microabrasion-corrosion test starts due to the partial rupture of
the surface oxide lm by abrasion and the subsequent exposure of
the metal surface to the chloride solution. Recorded current level
increases with the SiC volume fraction. For the 0.120 and
0.072 vol% the current level increases gradually during the
whole test. However, a slight decrease in the current noise level
is noticed after 400 s in the case of the 0.030 vol%, the detailed
30
SiC Al2O3
25
20
Current / A
15
10
5
0
0 200 400 600 800 1000
Time / s
Fig. 10. Typical current-noise curves of cast CoCrMo at 0.072 vol% abrasive
concentration.
 ARTICLE IN PRESS
R.J.K. Wood et al. / Tribology International 43 (2010) 12181227 1225

reason for this remains unknown. The fact that the average
current level decreases with decreasing SiC volume concentration
may be due to the different competition between depassivation/
repassivation during the abrasion under various test conditions.
At relatively high SiC vol%, the higher number of entrained
particles could reduce the time for repassivation between particle
impacts/indents, and therefore the material has less chance to
repassivate.
The interdependence between the average current and SWR is
shown in Fig. 14. A linear correlation was found (R2 =0.9912) with a
slope of 3.36  1013 mA m  2 N  1. This linear correlation indicates
that the (percentage) contribution of the electrochemical volume
loss to the total wear loss due to the microabrasion-corrosion
process remains the same although test condition changes.
Fig. 15 shows micrographs of the abrasion-corrosion wear
scars for different concentrations of SiC. Fig. 15(a) shows three-
body rolling damage dominates while Fig. 15(b) shows both
indentation damage and grooving indicating a mixed two/three-
body mode occurs at 0.072% SiC. Lowering the concentration
further to 0.03% changes the abrasive mechanism to
predominately two-body grooving as seen in Fig. 15(c).
Fig. 15(d) shows the scar for pure sliding under the no abrasive
case and only light polishing and some light scratches created by
asperities on the ball are seen. The level of indentation (rolling) in
the contact, therefore, seems to correlate with the average current
measurements.
Fig. 16 compares the predominately mechanical wear and
corrosion current induced for the four metallic surfaces
investigated. Four different trends are seen with the corrosion of
the sprayed surface being insensitive to wear rate until
1.5  10  12 m3 N  1 m  1 then increased currents are seen with a
slope of 3  1013 mA m  2 N  1. The cast CoCrMo has two

30
SiC 80.0
25 Al2O3
70.0
Average current / A

20 60.0

Current / A
50.0 0.00 vol %
15 40.0 0.030 vol %
0.072 vol %
Decreasing slurry vol.% 30.0
10 0.120 vol %
Decreasing slurry vol.% 20.0

5 10.0
0.0
0 200 400 600 800 1000
0
0 5.0x10 -13
10 -12
1.5x10 -12
2.0x10 -12
2.5x10 -12 Time / s
SWR / m3 N-1 m-1 Fig. 13. Typical current-noise curves for UNS S32205 duplex stainless steel at
different SiC abrasive concentrations in 3.5% NaCl solutions.
Fig. 11. Average current and SWR relationship for cast CoCrMo.

Fig. 12. Wear scars on cast CoCrMo produced by (a) 0.238 vol% SiC, (b) 0.072 vol% SiC, (c) 0.238 vol% Al2O3 and (d) 0.072 vol% Al2O3.
 ARTICLE IN PRESS
1226 R.J.K. Wood et al. / Tribology International 43 (2010) 12181227

sensitivities (slopes of 1 and 2  1013 mA m  2 N  1) but has lower
corrosion levels compared with the 2205 duplex steel with a slope
of 3  1013 mA m  2 N  1. The sintered WC-CoCr has a near vertical
trend with the corrosion rates varying without altering the wear
rate. The slopes associated with the sprayed WC-CoCr coating, the
cast CoCrMo and 2205 duplex stainless steel may reect
the tenacity of repassivation on the materials within the
environments tested. However, the currents measured are likely
to be from mechanically mixed layers or microstructurally
affected regions within the wear scar. Thus, further work is
required to identify these tribologically induced surface
microstructural and compositional changes to better understand
the signicance of these slopes.
70
0.12 vol.%
60
This type of representation does not mask the physical
meaning of the abrasion-corrosion data and is perhaps a better
way to present the results compared with quantifying synergistic
levels or percentages of the total wall wastage due to synergistic
terms which are difcult for the designers to use. The errors bars
seen in both x and y axes in Fig. 16 show the extent of data
variation within each test.
The analysis, thus far, has focused on the average current levels
but the uctuations around the mean values (standard deviation)
were also noted to vary and could be related to the depassivation/
repassivation activity within the wear scar as well as with the
wear mechanismelectrochemical interactions. The 2 Hz current-
noise sampling rate used (approximately twice per revolution of
the ball) meant that individual abrasive indents or grooves could
not be resolved. Thus further work is required to investigate this
observation and tests with increased sampling rates are required
coupled with more detailed understanding of the degradation
processes occurring within the scar.

0.072 vol.%
Average current / A

50
Decreasing slurry vol %
4. Summary
40
The present study shows that the abrasion-corrosion response
of sintered and thermally sprayed WC-CoCr, Cast CoCrMo and
30
0.03 vol.%
2205 duplex stainless steel can be dependent on the test solution
Decreasing slurry vol.%
chemistry, type of abrasives and the abrasive wear mechanisms.
20 The in situ electrochemical current-noise indicates the rate and
corrosion process of the material as abrasive wear progresses. It
10 also indicates susceptibility to corrosion under abrasive wear and
Pure sliding the extent and effectiveness of passivity/repassivation. Plots of
0 interdependence between predominately mechanical processes
0 5.0x10-13 10-12 1.5x10-12 2.0x10-12 2.5x10-12 (SWRs) and electrochemical processes (mean current level)
SWR / m3 N-1 m-1 against different testing parameters can be useful to interpret
wear-corrosion performance. Four different trends are seen with
Fig. 14. Average current and SWR relationship for the UNS S32205 duplex
the tribocorrosion of the sprayed surface being insensitive to
stainless steel in 3.5% NaCl.
current levels associated with passivation until 1.5  10  12 m3

Fig. 15. Wear scar of 2205 duplex stainless steel produced by (a) 0.12 vol% SiC, (b) 0.072 vol% SiC, (c) 0.03 vol% SiC and (d) pure sliding (without abrasives).

R.J.K. Wood et al. / Tribology International 43 (2010) 12181227
70
60
50
Average current / A
40
30
y = 2x1013x - 1.376
20
10
0
0 5.0x10-13
SWR / m3 N-1 m-1
Fig. 16. Current versus SWR for sintered WC-5.7Co0.3Cr hard metal, sprayed WC-10Co4Cr coating, UNS S32205 duplex stainless steel and cast F-75 CoCrMo.
N  1 m  1 then increased currents are seen with a slope of
3  1013 mA m  2 N  1. The cast CoCrMo has two sensitivities
depending on particle size and the number of particles entrained
into the contact (slopes of 1 and 2  1013 mA m  2 N  1) but has
lower corrosion levels compared with the 2205 duplex steel with
a slope of 3  1013 mA m  2 N  1. The sintered WC-CoCr has a near
vertical trend with the corrosion rates varying without altering
the wear rate due to the skeletal nature of the carbides only
allowing corrosion of the near surface binder phases between
surface carbides. The slopes associated with the sprayed WC-CoCr
coating, the cast CoCrMo and 2205 duplex stainless steel may
reect the tenacity of repassivation on the materials within the
environments tested. The current levels observed on all four
materials appear related to the number of indents (frequency or
rate) generated in 3-body abrasion and the repassivation time of
the worn surface. Owing to the close proximity of the carbides on
the surface of the sintered WC-CoCr, crevice type corrosion
developed within the localized environments between surface
carbides once the binder had been removed or dissolved. This
resulted in the current levels remaining high after the tribocorro-
sion tests. This was not seen for the other surfaces tested as they
had dispersed carbides and current levels returned to pre-test
levels after testing.
The predominately mechanical versus electrochemical repre-
sentations can serve as tools to better understand and predict
performance and design surfaces for various tribo-corrosion
systems. The representation also has advantages over the present
practice of running multiple tests to determine various synergis-
tic, antagonistic and additive terms and there quantication
which involves introducing signicant errors and uncertainties.
This approach has also been shown to cause difculty in material
selection and life prediction for wear-corrosion applications. Thus
the mechano-electrochemical plots may offer advantages when
dealing with surfaces subjected to tribocorrosion.
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