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a,*
c,*
Abstract
The literature dealing with the electrochemical corrosion characteristics of unalloyed copper
in aqueous chloride media is examined. The enormous quantity of polarisation and mixed/
corrosion potential data that has been made available in the literature over the last 50 years
has been compiled and discussed in a comprehensive review. For a wide range of electrode
geometries, the importance of the chloride ion and the mass transport of anodic corrosion
products on the corrosion behaviour of copper are made clear for both freshly polished and
lmed surfaces.
2003 Elsevier Ltd. All rights reserved.
Keywords: A. Copper; B. Polarisation; RDE/RCE; C. Oxygen reduction
1. Introduction
Pure copper is rarely used as a corrosion resistant material within the marine
environment. Copper-based alloys, however, such as the copper nickels, aluminium
bronzes and nickel aluminium bronzes, have an extensive range of marine applications [13]. Since the turn of the century, the corrosion of copper and its alloys has
been widely studied in chloride media where it has been observed that the chloride
*
Corresponding authors. Tel.: +61-7-3365-3668; fax: +61-7-3365-4799 (G. Kear), tel.: +44-1225-383488; fax: +44-1225-826-894 (F.C. Walsh).
E-mail addresses: garethkear@uq.edu.au (G. Kear), f.c.walsh@bath.ac.uk (F.C. Walsh).
0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0010-938X(02)00257-3
110
ion has a strong inuence on the copper corrosion mechanism. The main focus of
this review is the literature dealing with the electrochemical characteristics of the
copper metal/chloride corrosion system. An enormous quantity of research is
available on this subject and although most authors provide a necessarily limited
background to their own work, a comprehensive review has not been made available.
The discussion here, however, has been strictly limited to pure copper. The main
aspects of the work considered here include:
1. Measurement and characterisation of the anodic and cathodic reactions.
2. The inuence of solid surface species (produced via pre-treatment or in situ) on
reaction rates and mechanisms.
3. The derivation and replication of corrosion potential characteristics.
The inuence of mass transport conditions on the rate of the copper electrodissolution reaction is of particular interest to corrosion scientists and applied
electrochemists. This is particularly so for chloride ion concentrations roughly
equivalent to that of seawater ([Cl ] @ 0.50.6 mol dm3 or 3.03.6% w/v NaCl). The
anodic reaction has generally been taken to be reversible, mainly due to the rapid,
highly thermodynamically favourable complexation of the cuprous ion by the
chloride ion. The cathodic reaction, however, is dominated by oxygen reduction,
which is usually assumed to be relatively irreversible (hydrogen evolution usually
only becomes signicant at potentials more negative than )1.0 V vs. SCE). Thus,
with particular attention to the anodic reaction, the corrosion system has been
analysed with a number of ow geometries including the rotating disc and cylinder
electrodes, pipe and channel loops and the impinging jet. The inuence of both
natural and articial lm formation on the anodic and cathodic reactions is also
important as copper and copper alloys are generally only viable as corrosion resistant materials when in the passive state. At such lmed or blocked surfaces
transport processes occurring through poorly conducting solid corrosion product
layers limit both the overall anodic and cathodic reaction rates.
2. General corrosion
Early investigations of Bengough et al., in 1920 [4] and Bengough and May, in
1924 [5] studied the corrosion of copper in seawater as part of a series of reports to
the Institute of Metals. They determined that mature, protective scales formed at
the surface of copper consist largely, but not entirely, of corrosion products. They
assumed that in neutral chloride solutions, the main, initial corrosion product of
copper is cuprous chloride, CuCl formed via reaction (1).
Cu Cl ! CuCl
It was proposed that the cuprous chloride, which is only slightly soluble in dilute sodium chloride, reacts to produce cuprous oxide (cuprite) which was the
main constituent of thick scales [5]. The cuprous oxide was generally oxidised over
111
Chloride solution
Atacamite (Cu 2(OH)3 Cl) or malachite (CuCO3 .Cu(OH)2 )
Cupric hydroxide Cu(OH)2 or oxide (CuO)
Cuprous oxide (Cu 2O)
Cuprous chloride (CuCl)
Copper metal
Fig. 1. General stratication scheme of species in a mature copper corrosion product lm in seawater,
after Bengough et al. [4].
K1
CuCl
2
2
Cu Cl
2
3
Bianchi et al. [8] incorporated K1 (shown in Eq. (3) for 35& seawater at 25 C), to
place CuCl
2 as the main cuprous chloride complex in seawater and NaCl electrolytes
with [Cl ] concentrations approximating 0.55 mol dm3 . This is in agreement with
most authors [623].
The method of cuprous oxide production in the presence of the chloride ion is
usually taken as a precipitation reaction [8,17] rather than a direct electrochemical or
chemical formation from the base metal or cuprous chloride. The equilibrium in
reaction (4) is shifted to the right as the local concentration of, for example, the
CuCl
2 complex (produced directly from the dissolution of copper metal or CuCl)
increases and cuprous oxide is deposited in response.
2CuCl
2 2OH () Cu2 O H2 O 4Cl
112
Cl
2
2
CuCl
2 OH
1020
The stability of Cu2 O is inversely dependent on the concentration of chloride ions [8].
Thus, from the general literature dealing with copper corrosion, the rate of redissolution of the protective Cu2 O (as a soluble cuprous chloride complex) has been
shown to be much higher than that observed in chloride free, neutral/alkaline solution [5,8,24,25]. In a paper devoted to the thermodynamic stability of copper in
35& salinity seawater, Bianchi and Longhi [16], produced a number of equilibrium
potentialpH (Pourbaix) diagrams for the Cu/H2 O/Cl system which included the
inuence of carbonate and bicarbonate ions. An example has been reproduced in
Fig. 2, where the solid phases taken into consideration are Cu, Cu2 O, CuCl and
Cu2 (OH)3 Cl.
The majority of work in the literature is initiated either at polished surfaces or
pre-reduced surfaces. The composition and thickness of thermal and air formed
corrosion product lms, which form by oxidation of the metal during preparation/
storage should, therefore, be carefully considered. As will be seen in the later section
dealing with oxygen reduction, the presence of such lms can have considerable
inuence on reaction mechanisms. Preston and Bircumshaw [26] observed that, at
room temperature, the oxide lm on freshly polished copper consists only of a 2.5
nm thick cuprous oxide. No denite indication of the presence of cupric oxide, CuO,
was found. Other workers have discovered, however, that when a copper surface is
heated in air, oxygen or water, a duplex lm forms where the primary component is
cuprous oxide with a lesser concentration of cupric oxide and/or cupric hydroxide,
Cu(OH)2 [25,2734].
1.2
CuO 22-
O2 /OH
CuO
Cu2(OH)3Cl
E (V/SHE)
0.8
2+
Cu
0.4
HCuO2-
CuCl
0.0
H /H2
Cu 2O
Cu
-0.4
10
12
14
pH
Fig. 2. EpH diagram for copper in seawater of salinity 35& at 25 C (assuming an activity of 104
cuprous and cupric ions in solution), after Bianchi and Longhi [16].
113
The choice of electrolyte has also been shown to have a critical inuence on the
electrochemistry of the corrosion system [20,35]. Chernov et al. [35] compared the
corrosion behaviour of copper in 3% w/v NaCl solution and natural seawater. They
revealed that, owing to the buering properties of seawater, the rate of formation of
cuprous oxide in seawater solution is lower, and the rate of generation of cuprous
complexes (and thus the general dissolution rate) is higher than in the NaCl solution.
From reaction (4), an increasing pH resulting from the oxygen reduction reaction
will favour the consumption of cuprous chloride complex to form cuprous oxide.
From Fig. 2, the greater thermodynamic stability of cuprous oxide over cuprous
chloride at neutral and alkaline pH values is clear. The buering properties of seawater (due to the presence of carbonate/bicarbonate and borate ions [16,36]), however, will act to limit any change in pH of the electrolyte adjacent to the active
surface.
114
Cathode
Anode
6
7
8
9
If a pore free, oxide lm is assumed, both ionic and electronic transport through the
corrosion product will be essential for the corrosion process to proceed. In terms of
doping [41], the introduction of lower-valent cations into a p-type semiconductor
will increase the electron hole concentration and decrease the cation vacancy concentration. Higher-valent cations will, of course produce the opposite eect, increasing the number of cation vacancies. Ionic transport is usually rate limiting in
terms of overall conductivity since electron and hole mobilities are generally much
greater than ionic mobility. Thus, the introduction of cations of increasing valency
such as Ni2 and Fe2 will act to proportionally increase the overall conductivity of
cuprous oxide.
4. Electro-dissolution
As previously noted, the anodic polarisation behaviour of pure copper in chloride
media has received considerable attention in the literature. The main dierence between models is the identity of the initial, electro-dissolution reaction/s of bare
copper. The reactions are generally thought to be reversible and all are universally
assumed to be under mixed (charge transfer and mass transport controlled) kinetics
close to the corrosion potential. The three possible cases are given in reactions (10)
(14) where ki is the rate constant for the reaction of interest.
Case 1
k1
Cu 2Cl () CuCl
2 1e
k1
10
115
Case 2
k2
Cu () Cu 1e
11
k2
k3
Cu 2Cl () CuCl
2
12
k3
Case 3
k4
13
k4
k5
14
k5
Cases 1 and 3 represent the direct formation of a cuprous chloride species from the
metal, while Case 2 involves the dissolution of copper as cuprous ion in the rst
instance. Table 1 gives a summary of authors who have worked in this eld and their
proposed mechanisms.
Anodic polarisation of copper at large overpotentials in chloride electrolytes results in E vs. log i curves typied by the schematic shown in Fig. 3 [6,7,17]. With
reference to this gure, typical anodic polarisation curves can be split into three main
regions of potential:
Section I: a potential region of apparent Tafel behaviour where mixed charge
transfer and mass transport controlling kinetics are usually assumed.
Section II: a potential window of lm formation leading to a maximum peak current density and subsequent lm or metal dissolution giving a limiting current
density.
Section III: a potential above which any increase in current density is due to the
formation of Cu(II) species.
Table 1
Review of authors showing choice of reaction scheme for the initial electro-dissolution reaction of unalloyed copper in chloride media
Case 1
Case 2
Case 3
Taylor [49]
Bianchi et al. [8]
Lush and Carr [50]
Braun and Nobe [7]
de Sanchez and Schirin [51]
Smyrl [52]
Wood and Fry [14]
Mansfeld et al. [15]
Wagner et al. [53]
Kear et al. [54]
116
0.2
E (V/SCE)
0.1
Section III.
0.0
-0.1
Section II.
-0.2
-0.3
Section I.
0.5
1.0
1.5
-2
log (i / mA cm )
Fig. 3. Typical anodic polarisation characteristics of copper in aqueous chloride media.
117
0.2
E (V/SCE)
0.1
0.0
-0.1
(5)
(4)
(3)
(2)
(1)
(6)
-0.2
-0.3
-0.4
5
-1
-2
log (i / A cm )
Fig. 4. Plots of E vs. log i for copper at aqueous NaCl concentrations of (1) 4.0, (2) 2.0, (3) 1.0, (4) 0.5, (5)
0.1 and (6) 4.0 mol dm3 , after Lal and Thirsk [58]. Curves (1)(5) were performed at 18 C and curve (6) at
60 C.
(a) The relation E vs. log i is linear with a slope close to 60 mV decade1 at a xed
rate of mass transport (uid velocity) and chloride concentration:
dE
59 mV decade1
16
d logi Cl ;298 K
(b) The i vs. x0:5 relation is linear with an origin close to zero at a xed applied
potential and chloride concentration:
di
Constant
17
dx0:5 Cl ;E
(c) The relation E vs. logi=x0:5 is linear with a slope equal or close to 60 mV
decade1 :
2
3
dE
7
6
59 mV decade1
18
4
5
di
d log
dx0:5
Cl ;298 K
The examples given in (b) and (c) above are in terms of angular velocity, x (rad s1 ),
of the rotating disc electrode (RDE) [6,11]. The extensive range of mathematical
descriptions of the complete electro-dissolution behaviour of copper in the apparent
Tafel region have been summarised in Table 2. The symbols D, dN , m, c and iL refer to
diusion coecient (m2 s1 ), Nernst diusion layer thickness (m), kinematic viscosity
(m2 s1 ), concentration (mol m3 ) and limiting current density (A m2 ), respectively.
aA and aC are the charge transfer coecients for the anodic and cathodic reactions.
118
Table 2
Review of expressions derived to reproduce the electro-dissolution behaviour of copper in chloride media
at low positive overpotentials
Author/s
Notes
Bacarella and
Griess [45]
Case 1,
reversible
reaction
iF
Case 1,
reversible
reaction
DCuCl2
FE
Cl 2 exp
RT
dN
F Ee Ee0
zF x0:5 0:667
DCuCl Cl 3 exp
0:667
2
RT
1:61m
Moreau [11]
Case 3,
quasi-reversible reaction
1
aC FE
1
exp
;
k2
RT
BU n
iL
where B
expFE=RT
!
,
k5 k4
FE
dN
2
1
Cl exp
i
k5
RT
k4
DCuCl2
de Sanchez and
Schirin [12,51]
Case 2,
reversible
reaction
1:61D0:67
m0:167 x0:5
aA F
aC F
Cu
g
k
g
exp
i zFcv0
k2 exp
2
v0
Cu
RT
RT
cCu
Brossard [10]
Case 1,
reversible
reaction
F E E0
RT
Case 1,
reversible
reaction
,
a1 FE
1
i Fk1 Cl exp
RT
dN
Case 1,
reversible
reaction
i Fk1 exp
Case 2,
reversible
reaction
i Fk2 exp
Tribollet and
Newman [46]
Dhar et al. [20]
Smyrl [52]
Case 2,
reversible
reaction
Case 3,
quasi-reversible reaction
Case 3,
reversible
reaction
FE
RT
i exp
2
DCuCl2
k1 exp
a1 FE
RT
"
#
,
a1 F
dN
a1 F
g
1 k1
g
exp
RT
RT
DCuCl K2 Cl 2
2
,
a1 FE
1
RT
k2 dN
2
k2 Cl DCuCl2
exp
a1 FE
RT
k5 k4
FE
Cl exp
2
RT
k4
DCuCl2 0:667 m0:167 x0:5 1:62k5
0:167 0:5
FD0:667
x
CuCl m
9
8
FE >
>
>k4 exp
>
<
aA FE
RT =
i F k4 Cl exp
2
>
>
RT
>
>
;
: k4 k5 Cl
9
8
FE >
>
>
>
k
k
d
exp
< 4 5 N
RT =
>
>
:
k4 k5 Cl 2 DCuCl2
>
>
;
Case identities relate to Eqs. (10)(14). See the text for symbol meanings.
119
Although systematic reproduction of the derivations of each relationship is beyond the scope of this work, the main assumptions of each study can be summarised.
From Table 2, it is clear that the choice of anodic reaction (see case number) is
variable but it is usually taken to be reversible. With the exception of de Sanchez and
Schirin, who assume the direct dissolution to the free cupric ion (1982 and 1988),
the electro-dissolution current is always dependent on chloride ion concentration. If
only pure charge transfer controlled current density is considered (see again later in
this section), the rate dependency of the anodic reaction on the chloride ion can be
described via a classical kinetic equation:
m
i k zF Cl
19
where k is the potential dependent rate constant for the anodic reaction and m is the
reaction order with respect to the concentration of the chloride ion. Venkakachai
and Kannan postulated a value of 1.0 [59] for m while Faita et al. [17] have produced
a reaction order with respect to the chloride ion equal to 3. The most frequently
quoted value of m at NaCl concentrations less than 1.0 mol dm3 (7% w/v NaCl),
however, is 2.0 [6,11,18,45,46,52,56].
In all of the cases shown in Table 2, the anodic current is clearly dependent on
both charge transfer and mass transport. The diusion of CuCl
2 away from the
electrode surface is usually taken to control the mass transport controlled component of the current and H and OH ions are not directly involved in the dissolution
process. Consequently, the pH of the solution should exert no inuence over the rate
of electro-dissolution within the apparent Tafel region. This has been veried experimentally by Brossard [10]. It has also been noted that within the region of apparent Tafel behaviour, the polarisation behaviour of copper in acid chloride
solution is very similar to that in neutral chloride solution [6,7,9].
Dhar et al. [20] assumed that copper corrodes directly via the anodic dissolution
mechanism in Case 1, reaction (10), which was taken to be reversible. At high anodic
currents, when the overall rate of the anodic reaction is much faster than the diffusion rate of CuCl
2 (when mass transport will inuence the measured current), the
following expression was derived to describe the apparent Tafel behaviour:
dg
2:303RT
d logi a1 a1 F
20
where a1 and a1 are the charge transfer coecients for the forward and reverse
directions of reaction (10) in Case 1. Eq. (20) at 25 C predicts the 60 mV decade1 E
vs. log i response within the apparent Tafel region. Similar relationships have also
been produced by de Sanchez and Schirin [51], Eqs. (21) and (22).
d log di1 =dkm1
zF
1=59 mV decade1
2:3RT
dE
21
d logdi1 =dx0:5
zF
1=59 mV decade1
dE
2:3RT
22
120
Slopes of g vs. log i for copper [13] and copper alloy [51] dissolution in seawater was
found to be close to 1/60 decade mV1 (or 60 mV decade1 ). Note that the value of
z 1 and the charge transfer coecient has been omitted. For lmed surfaces, Wood
et al. [13] found that the directly measured anodic Tafel slope for copper changed to
values corresponding to an activated electron transfer rate determining step. That is,
where the transfer coecient, aA , is approximately equal to 0.5 (rather than zero for
a freshly polished copper surface) which produced a Tafel slope of 110 mV decade1 .
For this case, the kinetics of charge transfer had decreased to a level where mass
transport no longer inuenced the rate of electro-dissolution and, therefore, the
value of the Tafel slope. Lush and Carr [50] noted that an increase in the apparent
anodic Tafel slope from approximately 60 mV decade1 (at low ow velocity and low
overpotential) to 90 mV decade1 (high ow velocity and high overpotential) was
produced by a change in the balance between charge transfer and mass transport
control. This eect was said to be not due to a change in the mechanism of the
copper dissolution reaction itself. It was proposed that at high ow velocity, the
diusion of ions can be enhanced to such an extent that the charge transfer controlled component of the anodic reaction scheme becomes signicant and inuences
the measured current response. It appears that at high rates of mass transport the
charge transfer coecient will become signicant and inuence the apparent Tafel
slope value. That is, the observed change in the anodic Tafel slope from 60 towards
120 mV decade1 corresponded to a change in the value of the charge transfer coecient (for a single electron transfer) from 0 to 0.5.
Some evidence for the above has been noted in the literature for pure charge
transfer controlled Tafel slopes measured for copper in chloride media. The extraction of pure charge transfer controlled current from mixed controlled current
may be extracted using the KouteckyLevich equation approach [13,54,60,61]. For
cases where aA 0:5 has been assumed, Tribollet and Newman [46] and Smyrl [52]
have quoted pure charge transfer controlled Tafel slopes of approximately 0.120
V decade1 . Kear et al. [54] measured slopes of 0.062 and 0.097 V decade1 in ltered
and articial seawaters, respectively.
Section II of the anodic polarisation response will now be considered, where a
region of peak current density and limiting current density is usually observed.
Returning to Fig. 4, Lal and Thirsk [58] assumed that for neutral solutions, a surface
adsorbed precipitate of CuCl was formed at critical current densities, the values of
which were dependent on chloride concentration and temperature (later conrmed
by Venkatachari and Kannan [59], and Wagner et al. [53]). Once the deposition of
this precipitate reached a critical rate, the current attained a xed value i.e., a region
of limiting current density. Nobe and coworkers [6,7] produced a model explaining
the entire anodic polarisation response of copper in acid chloride solution. Again, it
is apparent that the model can equally be applied to neutral and alkaline chloride
media where Cu2 O precipitation may be favoured over the deposition of CuCl [17].
The peak maximum, minimum and limiting current density responses observed in
Section II are produced as the formation of CuCl becomes faster than either its
complexion by the chloride ion or mass transport of the cuprous dichloride complex
to the bulk solution. The apex peak current, therefore, is followed by a current
121
minimum as surface CuCl coverage reaches its maximum [22,23,55]. Further reaction
of the copper with chloride ions to form CuCl is reduced to a rate which Braun and
Nobe proposed as equal to the rate of Cl diusion from the bulk of the electrolyte
to the electrode surface [7]. The peak current maximum and the current minimum
were not observed for [Cl ] P 2.0 mol dm3 due to the high dissolution rate of the
cuprous chloride where a lm free surface can be assumed.
As predicted by the Levich equation [62] which describes current at a rotating disc
electrode under full mass transport control, Braun and Nobe [7] found that the
magnitude of the limiting current density was dependent on the angular velocity of
the disc according to x0:5 . Using the rotating ring disc electrode [6] it was found that
the formation of CuCl
2 was constant with increasing potential for a given chloride
ion concentration. This indicated that the maximum rate of CuCl dissolution had
been reached which was independent of potential. The limiting current density was
given by:
iL
0:167 0:5
0:62zFD0:667
x Cl
Cl m
1 tCl
23
where tCl is the transference number of the chloride ion. This is in agreement with
the general case of passivating lm formation in conjunction with lm dissolution
[67]. It is probable, however, that at these potentials, the limiting current density is
controlled by the diusion of the cuprous complex away from the surface of the
cuprous chloride to the bulk of the electrolyte [68]. For this model, Eq. (24) will hold.
iL
0:167 0:5
0:62zFD0:667
x CuCl
CuCl m
2
2
1 tCuCl2
24
Data produced by Kear [68], which considered the anodic polarisation of copper,
strongly indicate that limiting current densities, taken from plots such as those
shown in Fig. 5, are the result of cuprous dichloride ion mass transport. Literature
values for the diusion coecients of CuCl
2 and Cl ions are shown in Table 4,
where it is apparent that low diusion coecient values and relatively low concentrations of the cuprous complex compared to the chloride ion will tend to give rise to
a mass transport limiting step in the lm dissolution mechanism.
At potentials more positive than the limiting current region, P0.05 V vs. SCE
(Section III, Fig. 3), both the cuprous chloride complex and free cupric ions are
produced from surface cuprous chloride via competing reactions [6]. In this region, a
combination of the diusion of both Cu(I) and Cu(II) species from the electrode/
electrolyte interface into the bulk solution were said to be rate determining.
5. Cathodic polarisation
A simplied relationship for the complete reduction of oxygen, reaction (25),
involves an overall exchange of four electrons resulting in the production of hydroxyl
ions or, at low pH, water molecules.
O2 2H2 O 4e ! 4OH
25
Flow geometry
Temperature (C)
Surface condition
bA (V decade1 )
Reference
NaCl
RDE
28 1
Freshly polished
[59]
NaCl
NaCl
Static
Static
Freshly polished
Freshly polished
NaCl
NaCl
Static
Pipe ow
0.16 m s1 y
1.60 m s1 z
RDE
18
30100y
>100z
30175
20
25
Freshly polished
0.045 (0 rpm)
0.040 (500 rpm)
0.035 (1000 rpm)
0.040 (2500 rpm)
0.070 (5000 rpm)
0.055 0.005
@ 0.060y
0.1400.160z
@ 0.060
0.060y low g
0.070y high g
0.090z high g
0.064| (500 rpm)
0.053| (1000 rpm)
0.054| (1600 rpm)
0.067| (2500 rpm)
All slopes 0.005
@ 0.060 (03000 rpm)
Low g high g
0.063 0.063y
0.060 0.120z (8 m s1 )
0.061 0.130z (14.7 m s1 )
0.120 50y at low g
0.115 58z (2 m s1 )
0.038 0.047 (0 285 rpm)
0.062 0.065 (0 285 rpm)
@ 0.060 (slope independent of
exposure time)
0.067
0.087y and 0.098z
0.063 0.001y and
0.066 0.002z
NaCl| and
articial seawaterr
Freshly polished
Freshly polished
NaCl
Seawater
RDE
Staticy
Enclosed
channel owz
2025
25
Freshly polished
Freshly polished
Filmed
Seawater
RCE
Natural and
articial seawaters
Seawater
Seawater
Naturaly and
articialz seawaters
RCE
Filmed (7 days)
Filmed (21 days)
Freshly polished
Static
20
30y and 50z
25 0.2
Freshly polished
Freshly polished
Freshly polished
RDE
[58]
[63]
[45]
[50]
[20]
[56]
[13]
[64]
[15]
[65]
[66]
[54]
Electrolyte
122
Table 3
A review of directly measured anodic apparent Tafel slopes for pure copper in fully aerated neutral 3.03.5% w/v NaCl and natural and articial seawaters
123
106.2
6500 rpm
i (mA cm-2)
70.8
35.4
200 rpm
0.0
-0.4
Cu - 1.0 mV s-1
-0.3
-0.2
-0.1
0.0
0.1
0.2
0.3
E (V/SCE)
Fig. 5. Anodic polarisation curves for the electro-dissolution of freshly polished copper in ltered seawater as a function of rotating disc electrode rotation rate, after Kear [68].
Table 4
Diusion coecients for the cuprous dichloride complex ion and the chloride ion in chloride media
DCuCl2 (cm2 s1 )
5
1.0 10
5.4 106
5.0 106
5.5 106
2.0 105
Electrolyte conditions
3
Reference
[11]
[46]
[13]
[18]
[36]
26
124
It is clear that the complete, four-electron reduction of oxygen may occur through
a direct or indirect route. Hydroxyl ions or water molecules can be products of a
single four-electron step or the result of cumulative two-electron reduction steps
where oxygen is reduced to peroxide which in turn is reduced to hydroxyl ions.
Hence, if k6 , k10 , k9 are small and k8 , k9 large, oxygen reduction may only involve an
overall two-electron change. Clearly, this explanation is simplied. The kinetics of
the reversible electrochemical and chemical reactions along with the rates of the
adsorption/desorption processes may be equivalent to the active reduction processes.
This will result in a complication of the overall reduction mechanism. Because of
these considerations, the kinetics of oxygen reduction are expected to be very specic
to the system under study. This is found to be the case in practice [69]. The character
of the substrate, surface condition, temperature and electrolyte conditions all have
an inuence over each step in the reduction mechanism.
The earliest study dealing with the reduction of dissolved oxygen at copper in
chloride media was performed by Delahay in 1950 [71]. Over the whole range of
negative overpotentials studied, it was determined from polarisation curves and
oxygen consumption data that the number of electrons consumed was predominantly four. Although hydrogen peroxide was always formed, it was proposed that a
form of catalytic decomposition prevented the build up of this intermediate reduction product. Balakrishnan and Venkatesan [72] incorporated the rotating ring disc
electrode (RRDE) in a full kinetic study of oxygen reduction at copper in sodium
chloride solution. The reaction was studied for both freshly polished and pre-reduced surfaces. Cathodic polarisation from Ecorr to )1.4 V vs. SCE produced a single
mass transport limited wave which was taken to indicate the absence of large
quantities of peroxide. These plots are similar to those measured by Kear et al. [54]
as a function of rotating disc electrode rotation rate (see Fig. 6). Here, (a) denotes
oxygen reduction under charge transfer/kinetic control, (b) oxygen reduction under
mixed mass and charge transfer control, (c) oxygen reduction under mass-transfer
control and (d) hydrogen evolution. Reverse scans measured by Balakrishnan
and Venkatesan, however, showed two distinct waves or peaks. The second peak
at @ )0.4 V only became noticeable only on a partially or completely oxide free
surface and was identied with the reduction of oxygen to hydrogen peroxide. This
has also been veried by Venkatachari and Kannan [59].
Deslouis et al. [56] found that the morphological characteristics of cathodic polarisation curves measured at copper are strongly dependent on the time of immersion prior to polarisation. Indeed, it is clear from the literature that at potential
sweep rates P1 mV s1 non-steady-state conditions can result at surfaces supporting
corrosion products. After an equilibration time of 5 min at 0 rpm, Deslouis et al.
found that LSV curves produced a peak superimposed upon the single wave for
125
0.0
(a)
i (mA cm-2)
-0.7
200 rpm
-1.3
(b)
-2.0
-2.7
(c)
-3.3
-4.0
-1.5
9500 rpm
(d)
-1.2
-0.9
-0.6
-0.3
0.0
E (V/SCE)
Fig. 6. Cathodic linear sweep voltammetry at the copper RDE as a function of angular velocity in aerated
ltered seawater at 25 0.2 C and a scan rate of 0.5 mV s1 , after Kear et al. [54].
27
28
126
Thus, the features of the reduction of oxygen at copper electrodes should be inuenced by a combination of the copper corrosion reaction, the Cu /H2 O2 reaction
and the normal kinetics of reduction at a bare copper surface. A study of the reduction of hydrogen peroxide at pre-reduced, polished and pre-oxidised copper in
the absence of oxygen by Vazquez et al. [24] conrmed that peroxide can be electrochemically reduced on articially oxidised surfaces containing Cu(I) species. In
the absence of chloride, the reduction process was catalysed by a redox cycle involving the Cu(I)/Cu(II) couple:
Cu2 O H2 O2 ! 2CuO H2 O 2e
29
30
31
Cu2 O H2 O2 ! 2CuO H2 O
32
Again, the cuprous oxide is regenerated electrochemically via the reduction of the
cupric oxide (reaction [30]). Oxygen reduction at corrosion product free copper was
examined using NH4 Cl as a Cu(I) complexing agent. Again, the eect was to produce
a more irreversible reduction process and to separate the linear sweep voltammetry
reduction waves for oxygen and peroxide.
King et al. [57] studied the reduction of oxygen at polished copper in neutral,
unbuered 1.0 mol dm3 NaCl using the RRDE at various oxygen concentrations.
They found that the reduction process was rst order with respect to oxygen concentration and as shown in reaction (33), following the adsorption of oxygen at the
electrode surface, the rst electron transfer is rate determining.
O2 1e ! O
2
33
The increase in interfacial pH due to the net production of hydroxyl ions in unbuered NaCl was said to favour the formation of the catalytic Cu(I) surface lm
127
and the overall reaction rate through catalytic Cu(OH)ads or Cu2 O species. They
found, however, that in the presence of Cu(I) surface lms, peroxide was detected as
a stable intermediate at the RRDE. The ring current was only signicant, however,
at low negative overpotentials and at a bubbling gas composition of 100% oxygen
where hydroxide production would be signicant. From this work, King et al. [57]
proposed a reduction mechanism similar to that of Schirin and Vazquez et al. involving oxygen reduction on two types of surface site having diering degrees of
reactivity. The most reactive site towards oxygen reduction involves a Cu(I) species.
The least reactive site is found at the metal itself, Cu(0). An overall expression for the
RDE geometry was derived where the catalytic Cu(I) species was taken to be
Cu(OH)ads , Eq. (34):
"
(
0:5
O2 exp
#)
a0A aC F
aC F
g
g
exp
RT
RT
34
where Ic:t: is the cathodic current due to charge transfer controlled oxygen reduction,
A is the surface area of the electrode, hA is the fractional surface coverage of bare
copper, a0A is the anodic transfer coecient for the formation of Cu(OH)ads . aC is the
cathodic transfer coecient and kCA and kCB are the electrochemical rate constants
for oxygen reduction at bare copper and Cu(I) lmed copper respectively. The term
Z is a constant in the Levich equation consisting of:
Z 0:64m0:167 D0:667
35
Ic:t:
aC F
g
zFAkCA O2 exp
RT
36
128
Table 5
Review of cathodic Tafel slopes for pure copper in aerated chloride media
Temperature (C)
Surface condition
bC (V decade1 )
Reference
30 0.1
[72]
25
[20]
Natural seawater
25
)0.5 to )0.3
)0.5 to )0.3
[13]
Natural seawater
28 1
20 1
)0.238y
)0.155z
)136| (500 rpm)
)194| (1000 rpm)
)195| (1600 rpm)
)173| (2500 rpm)
)192r (500 rpm)
)190r (1000 rpm)
)167r (1600 rpm)
)167r (2500 rpm)
All slopes 0.005
)0.150y
)0.210#
)0.035 to )0.075
)0.100 to )0.325#
(RDE: 0285 rpm)
)0.130 10
)0.30
Freshly polishedy
and pre-reducedz
Freshly polished
[59]
[69]
)0.046
@ )0.100
[65]
[15]
)0.13 (2.0% O2 + N2 )
)0.14 (5.0% O2 + N2 )
)0.15 (10.0% O2 + N2 )
)0.17 (20.9% O2 + N2 )
)0.17 (50% O2 + N2 )
)0.16 (100% O2 )
)0.134y
)0.148z
)0.70 to )0.35
)0.75 to )0.35
)0.75 to )0.35
)0.75 to )0.35
)0.90 to )0.50
)0.80 to )0.55
@ )0.50 to )0.65y
@ )0.50 to )0.65z
[57]
20
23 2
25 0.2
[64]
[54]
Electrolyte
Electrolyte
Electrode material
Temperature (C)
D25 C 105
(cm2 s1 )
Reference
Monel
Aluminium brass
Carbon steel
Range of CuNi
Cu
Cu and 7030 CuNi
Cu
25
20
20
30
2025
19
20
2.3
1.7
1.7
1.9
2.0
1.4
1.9
2.3
1.9
1.9
1.8
2.0
1.6
2.1
[76]
[51]
[77]
[78]
[56]
[12]
[74]
Cu
Cu
Cu
Marinel CuNi#
Cu
9010 CuNi#
Nickel aluminium bronze
23 2
23 1
20
1.7
1.8
1.4
1.5#
2.0y 2.2z
2.2y#
1.7y , 1.8z
1.8
1.9
1.5
1.7#
2.0y 2.2z
2.2y#
1.7y , 1.8z
[57]
[18]
[79]
25 0.2
[68]
Table 6
Literature diusion coecient values for oxygen at atmospheric pressure in chloride media
129
130
2> 1
Ecorr1
Ecorr2
A1
A2
C1
log icorr1 log icorr2
C2
log i
Fig. 7. Schematic polarisation curves for copper corrosion in aerated chloride media for two diering
mass-transfer conditions, x1 and x2 , after Faita et al. [17]. Anodic and cathodic polarisation curves are
represented by Ax and Cx respectively.
131
-0.240
E (V/SCE)
-0.260
200 rpm
-0.280
-0.300
9500 rpm
-0.320
Filtered seawater
-0.340
400
800
1200
1600
2000
t (s)
Fig. 8. Typical mean open circuit (corrosion) potential transients for freshly polished copper in aerated,
ltered seawater as a function of RDE rotation rate, after Kear et al. [54].
used to describe the corrosion process occurring at the copper surface. At the mixed
potential, the anodic dissolution of copper is under mixed charge transfer and mass
transport control within the apparent Tafel region and the cathodic reaction (oxygen
reduction) is under full charge transfer control. The increasingly negative corrosion
potential (Ecorr1 to Ecorr2 ) and derived corrosion rate (icorr1 to icorr2 ) is solely due to the
greater anodic current within the apparent Tafel region. Evidence for this increase in
negativity of the corrosion potential with uid velocity is given in Fig. 8 for copper in
ltered seawater [54]. From this data, it is clear that immediately after immersion of
a freshly polished electrode the magnitude of change in potential is dependent on
rotating disc electrode rotation rate.
As seen in the earlier section dealing with copper electro-dissolution, the greater
currents are due to increasing rates of cuprous dichloride complex mass transport at
increasingly greater RDE angular velocities (from x1 to x2 ). With varying degrees of
acknowledgement to the work of Faita et al., this model has been adopted by a
number of other workers [18,50,51,54]. Of note, both Lush and Carr [50] and
Schirin and coworkers [13,51] predicted that the corrosion potential would become
independent of the rate of mass transport at high uid velocities and the latter authors derived expressions that are able to reproduce Ecorr [51] and icorr [13]. For a fair
estimation of the corrosion rate, de Sanchez and Schirin [51] suggested employment
of the activated Tafel oxygen reduction polarisation curve combined with measurement of the open circuit at various rotation rates. This direct method was suggested to avoid the laborious calculation of the electrochemical constants and errors
associated with changes in surface condition during anodic linear sweep voltammetry. The latter problem, however, can be eliminated with the use of a potential
step, current transient technique [54,81].
132
In a 1995 study of the corrosion of copper in 1.0 mol dm3 NaCl, King et al. [18]
used the RDE as a function of oxygen concentration and mass-transfer coecient.
They demonstrated that only with a signicant decrease in the bulk oxygen concentration, did the cathodic reaction exhibit mixed charge and mass transfer control at
the corrosion potential. But, complete charge transfer control of the anodic reaction
was only predicted at very high RDE rotation frequencies, f , in excess of @ 1 kHz
(60,000 rpm). This extremely high value of rotation rate indicates the importance of
mass transport in their model. The eect of a covering layer of porous nylon membrane or compacted clay (to reduce the mass-transfer coecients of O2 and CuCl
2)
was to produce total charge transfer control of both the anodic and cathodic reactions
at the mixed corrosion potential. This was taken as a simulation of the eect porous
and micro-porous surface lms would have on the corrosion mechanism at the mixed
potential. The dependence of the steady-state corrosion potential as a function of
RDE rotation rate and oxygen concentration is shown in Table 7 [18].
From this table, it can be seen that the corrosion potential becomes less dependent
on rotation rate with decreasing oxygen concentration and consequently, the negative slope of Ecorr vs. logarithmic (electrode frequency) becomes more positive. At
very low oxygen concentrations, both the anodic and the cathodic processes are
inuenced by changes in the conditions of mass transport which will have a tendency
of cancel the rotation rate eect. Full mass transport control of the oxygen reduction
reaction was not achieved, however, even for the fully de-aerated electrolyte, due to
the irreversible nature of oxygen reduction at copper.
Several studies have also been made using linear polarisation resistance, Rp in
conjunction with the SternGeary relationship, Eq. (37) [84], where the mixed
controlled, apparent Tafel slopes for the anodic reaction are usually taken for the
term bA .
icorr
bA bC
B
2:3Rp bA bC Rp
37
dEcorr
vs. SCE
d logf
(V)
dEcorr
vs.
d logO2
SCE (V)
1.0
1.0
1.0
1.0
0.1
)0.306 0.008
)0.356 0.011
)0.413 0.011
)0.426 0.014
)0.246 0.007
)0.019
)0.015
)0.014
)0.011
)0.016
0.049
0.057
0.032
133
Table 8
Values of the proportionality constant, B, for unalloyed copper in chloride media
Electrolyte
Value of B (V)
Reference
Natural seawater
3% NaCl
Natural seawater
33.5% NaCl and natural seawater
Naturaly and articialz seawaters
Naturaly and articialz seawaters
0.006
0.031
0.005
0.019 0.001
0.014y and 0.020z
0.018 0.001y and 0.023 0.003z
[82]
[82]
[83]
[20]
[15]
[68]
7. Conclusions
Four general conclusions can be drawn from the literature dealing with the
electrochemical corrosion of lm free copper in chloride media:
1. At potentials close to the corrosion potential the anodic reaction is under mixed
charge transfer and mass transport controlling kinetics where the mass transport
limiting step is the rate of movement of a cuprous chloride complex away from the
electrode surface to the bulk electrolyte.
2. The cathodic reaction is dominated by the comparatively irreversible reduction of
oxygen via either a two- or four-electron exchange which remains under complete
charge transfer control at potentials close to the corrosion potential.
3. At the corrosion (mixed) potential the anodic reaction is under mixed control
while oxygen reduction is under pure charge transfer control and, as such, the corrosion rate is dependent on mass transport conditions.
4. The corrosion of copper in aqueous chloride media is made complicated by the
formation of surface lms.
5. The presence of surface lms generally act to reduce the rate of both anodic and
cathodic charge transfer process and, as a result, the inuence of mass transport at
the corrosion potential reduces in importance.
Acknowledgements
The authors are grateful to Dr. Carlos Ponce de Leon for editorial assistance
during the preparation of this review.
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