1.
Introduction
Pitting corrosion of
copper in chloride
solutions
A. El Warraky
H.A. El Shayeb and
E.M. Sherif
The authors
A. El Warraky, H.A. El Shayeb and E.M. Sherif are based
at the Laboratory of Electrochemistry and Corrosion, National
Research Centre, Dokki, Cairo, Egypt.
Keywords
Copper, Corrosion, Pitting corrosion, Chloride
Abstract
The pitting corrosion of copper in chloride solution has been
studied using potentiostatic polarisation and surface analysis
techniques. X-ray photoelectron spectroscopy (XPS) results
enabled conclusions to be drawn about the nature of the film
formed in different chloride concentrations. In dilute chloride
solutions C # 1023 M; XPS proved the existence of Cu2O
film on the copper surface. It was found that, depending on
the chloride content, pitting of copper was evident only after
the formation of a protective film of Cu2O. A current-time
trend plot showed the onset of fluctuations, which were
dependent on the NaCl content. On the other hand,
introduction of O2 into the solution during prepolarisation
time period increased the current value of the fluctuations at
the same concentration of NaCl in comparison with the freely
aerated solution. These results, together with the surface
analysis, confirm the role of chloride ion on the mechanism of
pitting attack on copper metal.
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Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 pp. 5261
q Emerald Group Publishing Limited ISSN 0003-5599
DOI 10.1108/00035590410512735
52
Copper has been one of the preferred materials
for transport of water in domestic and industrial
water utilities, in plumbing within buildings and
heat exchangers, etc. However, under some
exceptional conditions, pitting corrosion of
copper may occur, especially in the presence of
certain anions such as chloride, bicarbonate,
sulphate, nitrate and others. Several authors
(Adeloju and Daun, 1994; Adeloju and Hughes,
1986; Al-Kharafi et al., 1989; Beckon and
Baines, 1955; Campbell, 1974; Cornwell et al.,
1973; Drogowska et al., 1992; Linder, 1988;
Lucey, 1965, 1972; Mattsson, 1987; Shalaby
et al., 1989) studied the pitting corrosion of
copper and copper alloys in chloride solutions.
Each of them examined the issue from different
viewpoints and with different experimental
treatments, in the presence of various anions.
Some authors (Adeloju and Hughes, 1986;
Drogowska et al., 1992; Linder, 1988;
Mattsson, 1987) were of the opinion, based on
electrochemical measurements, that the pitting
corrosion of Cu occurred after the formation of
stable basic copper carbonate film (CuCO3 Cu
(OH)2). Other studies (Adeloju and Hughes,
1986; De Chiavlo et al., 1985; Ord et al., 1987)
demonstrated that copper oxide films were
formed before the formation of the bicarbonate
salt. All of the above studies were carried out in
the presence of various anions, such as sulphate
(SO22 2
4 ), bicarbonate (HCO3 ), nitrate (NO3 )
2
2
and perchlorate (ClO4 ). The results (Shalaby
et al., 1990) showed that bicarbonate ions do
not play a role in the initiation of pitting,
whereas sulphate and chloride ions are the main
cause of pitting corrosion. Other workers
(Edwards et al., 1994) reported that SO22 4
seemed to induce pitting, whereas Cl2 tended
to passivate the surface.
X-ray photoelectron spectroscopy (XPS)
studies (Kautek and Gordon, 1990) of anodic
copper surface film showed the appearance of a
characteristic band of Cu2O, and there was no
evidence of a CuO response. At higher anodic
potential, the non-detection of CuO suggests
that the second oxidation state does not change
the initial Cu2O film formed. The above result is
in good agreement with the results of in situ
Raman work (Hamilton et al., 1986), which
showed that the two oxidation states were
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
resolved, depending on the applied potential.
The first was the formation of Cu2O, while the
second represents that of Cu(OH)2.
A few papers (Duthil et al., 1996;
Kristiansen, 1981; Qafsaoui et al., 1993)
studied the pitting corrosion of copper after
equilibrating the sample potentiostatically in
borate-buffered solution for sufficient time to
allow the development of the oxide film. The
results of XPS surface analysis confirmed that
the passive film was composed of two layers, the
outer layer being CuO, while the inner was
Cu2O (Chawla et al., 1992; El-Tantawy et al.,
1981; Lenglet et al., 1990). The outer layer of
CuO disappeared and the stable Cu2O (the
inner layer) remained where conditions for
pitting corrosion became favourable.
From the above, the combined effects of the
various anions remained unclear, and it was the
purpose of the present investigation to solve this
controversy. Thus, Cu behaviour in NaCl alone
had to be investigated in a freely-aerated and
oxygenated solution of NaCl (102 5-102 1 M) to
form a Cu2O film at the Cu surface without the
addition of any anions.
2. Experimental
The material used in this measurement was
copper containing (in per cent) 0.281 Zn, 0.01
Sn, 0.01 Ni, 0.019 Fe, 0.017 P, 0.005 As and
0.005 Pb. The electrodes were in the form of
sheet, with dimensions of 1 1 cm and 0.2 cm
in thickness. The exposed area of the Cu
electrode to the solution was ca. 2.5 cm2. Before
testing, specimens were abraded with emery
paper of increasing fineness up to 1,000, rinsed
in distilled water, degreased with acetone and
rewashed again with bi-distilled water.
Potentiostatic cyclic polarisation curves were
recorded in different concentrations of NaCl to
check the susceptibility to localised attack.
Before commencing the polarisation
measurements, the samples were kept at
2 600 mV versus saturated calomel reference
electrode (SCE) for 30 min in the test solution
to reduce the oxides on the surfaces.
The electrochemical cell was made of Pyrex
glass with three holes, in which the metal
electrode, a platinum auxiliary electrode and a
SCE were fitted. All solutions were prepared
from analar grade reagent and bi-distilled water.
53
Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
Polarisation was then carried out by changing
the potential of the electrode towards noble
values up to +1,000 mV with a scanning rate of
40 mV/min. The polarisation was then reversed
to negative potential values. The current was
recorded using a Wenking potentiostat model
POS 273.
Potentiostatic current-time tests were
carried out using a Potentiostat-Galvanostat
(Amel model 2053) with an X-Y recorder (Kipp
and Zonen) to monitor the current-time
behaviour of the copper electrode. Polarisation
was achieved by the application of a constant
potential value for a certain time period. Some
of the samples were taken for surface analysis,
where the samples were cleaned in bi-distilled
water for 15 min using ultrasonic vibration and
dried between fibreless tissue. Finally, the
sample was immediately introduced into the
vacuum chamber of a scanning electron
microscope (SEM: JSM T20 of JEOL Co. Ltd
Japan) and subjected to XPS for surface
analysis. Adjustment of the XPS spectrometer
procedures for measurement, and the analysis
conditions, were described in Saber and El
Warraky (1991).
3. Results and discussion
3.1 Potentiostatic polarisation
Cyclic polarisation measurements can give a
rapid and reliable information about certain
types of corrosion phenomena and can
sometimes be the only way to investigate such
problems. Accordingly, the polarisation of
copper in NaCl was studied to gain an insight on
the electrochemical behaviour of Cu metal.
Figure 1 shows the cyclic polarisation curves
of copper in different concentrations of NaCl
from 102 5 to 102 1 M. At lower concentrations
C # 1024 MCl2 ; the polarisation curves show
anodic reactions which are essentially limited by
the applied potential. At such concentrations,
the chloride ions have a little significant effect.
The anodic reaction reveals that:
Cu Cu e2 1
Cu Cl2 CuCl 2
In such conditions, the oxide is probably formed
(Al Hajji and Reda, 1996) as:
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 1 Potentiostatic cyclic polarisation curves for copper in different concentrations of NaCl (forward ! solid line,
backward ! dotted line)
2CuCl H2 O Cu2 O 2H 2Cl2
The small variation in the values of current
recorded at 102 5 and 102 4 M Cl2 indicate that
healing and formation of the oxide probably
take place simultaneously.
As the concentration of NaCl was further
increased C $ 1023 M, the corrosion potential
of the copper electrode shifted to more negative
values and the anodic current attained higher
values with the increase of the Cl2 ion
concentration. These results were similar to the
findings of Shalaby et al. (1990), who reported
that very little current was produced during
potentiostatic polarisation of copper in <
102 3 M Cl2 solution. This was attributed to the
possibility of an ohmic potential drop that
resulted from the formation of a relatively
compact scale, and a build-up of corrosion
products under the scale. Earlier, Thomas and
Tiller (1972) reported that the film formed on
copper in 102 2 M NaCl does not offer effective
protection, and that protection is rapidly lost
under the influence of the chloride ions.
The present results showed that no pitting
was recorded after polarisation of copper in all
concentrations of chloride solution. At lower
concentrations C # 1024 ; an oxide film was
observed. XPS analysis of the sample shown in
Figure 2(a) identified Cu2O as a major
Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
3 constituent of the surface film. At higher
concentrations, especially at 102 1 M NaCl, the
initial active region was followed by the
appearance of anodic current peak. This
dissolution peak in the 102 1 M curve of
Figure 1, and the associated potentiostatic
pattern, were similar to that of passive metals,
though with a much higher dissolution current.
This curve was predicted earlier in every respect
(Langenegger and Robinson, 1968), except that
in their curve a second small peak was recorded
at a slightly more positive potential value than
that of the main dissolution peak. Several
authors (De Chiavlo et al., 1984; El Warraky
and El Dahan, 1997; Kautek and Gordon,
1990; Marchiano et al., 1980; Strehblow and
Titze, 1980) suggested that the first peak is
associated with the oxidation of copper to Cu
(I), while the second is due to the oxidation of
Cu (I) to Cu (II).
In view of the copper species identified on the
surface, using XPS technique, the dissolution of
copper at higher concentration of NaCl C $
1022 M can take place through the
electrochemical reactions of equations (1), (2)
and (4) (Bacarella and Griess, 1973; Bonfiglio
et al., 1973; Braun and Nobe, 1979; Brossard,
1983; Cooper and Bartlett, 1958; El Warraky,
1992; Lee and Nobe, 1986; Moreau, 1981;
Moreau et al., 1982; Walton and Brook, 1977):
54
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 2 XPS (XMM) peaks of copper species following polarisation at 400 mV
in (a) 102 4 M NaCl, and (b) 102 1 M NaCl
CuCl Cl2 CuCl2
2 4
In the presence of higher concentrations of
chloride, the formation of CuCl is a preferred
choice, rather than Cu2O formation which, if
formed, would oxidize to CuO. This latter
species was never detected from XPS multiplex
analysis (Figure 2(b)), indicating that the
predominant species present was CuCl, which is
not protective as is Cu2O. Hence, anodic
dissolution reaction of copper is under the
charge-transfer control, where the logarithm of
dissolution current of copper increases linearly
with potential. At higher potentials, the plateau
of current indicates a diffusion-limited rate,
probably because of the diffusion rate of copper
through the surface film of CuCl that is formed
on the copper surface (Alkire and Cangellari,
1989; Deslouis et al., 1988). Hence, the
dissolution of Cu in NaCl is quite uniform in
nature and there is no type of pitting corrosion.
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Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
3.2 Current-time measurements
Potentiostatic investigation of the I-E curves in
Figure 1 showed that this method alone was not
capable of providing precise information about
the pitting corrosion of Cu in NaCl solution.
The determination of the current density (CD)
vs time relationship at various constant
potentials, in combination with the use of
surface analysis, can provide more information
about the pitting corrosion behaviour of Cu in
freely aerated and oxygenated solution of NaCl.
3.2.1 In freely aerated NaCl
Measurements of the CD against time at
400 mV vs SCE for copper in different
concentrations of NaCl are shown in Figure 3.
An important feature of these curves is that, at
lower concentration of NaCl C , 1023 M, the
initial current begins at very low values and
decrease slightly with time until a steady-state
value was achieved, due to the formation of
Cu2O, as represented in equation (3) and
Figure 2(a).
In 102 3 M NaCl (Figure 3), a considerably
larger increase in current was recorded, and a
steady-state current was attained after some
initial undulations in the trace, as compared to
the low concentration C , 1023 M data.
This finding supported the fact that at higher
concentration, there is a competition between
the hydrolysis of CuCl formed to give the
compact and less soluble Cu2O (Bokris et al.,
1981; Charlot, 1954), as represented in
equation (3), and its dissolution through the
formation of CuCl2 2 (El Warraky, 1997; Sienke
and Plane, 1974), as described by equation (4).
At higher concentrations of NaCl,
C $ 1022 M, a further increase in CD was
recorded, depending on the concentration of
NaCl. The initial CD is higher, showing that at
102 2 M Cl2 , a slight increase in current was
evident at the first moment of immersion,
though with longer time there was some
decrease before a steady-state value was
achieved. On the other hand, at 102 1 M Cl2 ,
the initial CD increased at the moment of
immersion to a higher rate than was the case
with 102 2 M Cl2 , representing the dissolution
of the pre-immersion oxide film. The steady-
state current was attained at higher CD, and
increased again after 160 min, due to the
dissolution of the metal. This finding further
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 3 Current-time curves for copper in different concentrations of NaCl at 400 mV
supported the hypothesis of the formation of
CuCl as mentioned earlier, which does not
give the opportunity for hydrolysis to Cu2O,
but to dissolution in the form of CuCl2 2 as in
equation (4) and Figure 2(b). The formation of
CuCl is not sufficiently protective to prevent
attack and a steady-state dissolution rate is
established at higher CD. This observation
was explained (Mankowski et al., 1997) by
the formation of CuCl layer leading to its
dissolution as CuCl2.
This interpretation of observed phenomena
concurs with the results of the present
investigation of the formation of CuCl at higher
concentration of Cl2 , but the dissolution
behaviour is different. Figure 2(b) shows the
formation of CuCl, though the satellite peak
corresponding to Cu2+is not recorded for Cu
2P3/2 and Cu 2P1/2. From the above
observations, it is clear that dissolving CuCl
passes through the CuCl2 2 soluble complex and
is not due to the presence of soluble CuCl2.
The above results further support the general
dissolution of Cu in freely aerated NaCl
solution.
Further insight into the role of Cl2 could be
gained by immersion of copper coupons in
solutions of 102 4 M Cl2 for 30 min (i.e. where
the formation of Cu2O film is feasible).
Subsequently, only the solution was changed to
a higher concentration of 102 2-5 1021 (new
solution), and at this time, a constant potential
56
Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
of 400 mV was applied. In Figure 4, each curve
was obtained with the same pre-treated sample,
which was immersed in fresh solution
containing different concentrations of NaCl
from 102 2 to 5 1021 M at 400 mV.
These curves show that, on increasing the
concentration of NaCl from 5 1022 to
5 1021 M, a sharp decrease in the CD with
time occurred, depending on the concentration
of NaCl. At the first moment of immersion in
higher concentrations of NaCl (5 1021 M),
a larger drop in CD was observed, due to the
presence of an equilibrium between the
concentration of the adsorbed layer through the
pre-treatment in 102 4 M NaCl, and the higher
concentration of NaCl present. Then, a slow
rate of decrease in the CD occurred with time,
the degree of which was dependent on the
concentration of NaCl. This behaviour is
related to the influence of the Cu2O, formed
during the prepolarisation time in 102 4 M
NaCl. After these decreases in the current,
fluctuations were observed which extended to
the end of experiments. These fluctuations were
due to the formation of small pits, and are
dependent on the concentration of NaCl.
Figure 4 shows that at 5 1021 M NaCl,
a higher rate of fluctuations in the CD was
recorded and there was a slight increase in
the value of the current over time from 9 to
10 mA/cm2 at the end of the experiment.
The increase in the current was due to the
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 4 Current-time curves for copper in different concentrations of NaCl
at 400 mV after immersion of the sample in 102 4 M NaCl for 30 min pre-
polarisation time
initiation of pits, which is accompanied by
propagation of pitting at some locations.
A further insight into the pit initiation and
propagation was gained using the SEM
technique. The surface of the Cu sample at the
end of the experiment, in case of 5 1021 M
NaCl, is shown in Figure 5(a) and (b). The
SEM micrograph (Figure 5) shows fine pits
beside a large pit. This observation further
supports the observed amplitude of fluctuations
in the CD in case of 5 1021 M NaCl of
Figure 4, and the slight increase in total CD due
to the propagation of the pits at certain areas, as
in the case of the large pit shown in Figure 5(a).
On the other hand, the photograph of
Figure 5(b) represents the major part of the
surface, while Figure 5 (a) shows only localised
initiation of pits.
An important feature in both polarisation
curves of Figure 4, reinforced by the surface
appearance shown in Figure 5(a), is the slight
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Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
Figure 5 SEM of copper in 5 1021 M NaCl at the end of
experiment of Figure 4 in two different areas. (a) Pitting area,
and (b) general surface condition
increase in current during the fluctuation in
current, and the occurrence of a single large pit.
The total number of pits propagating on the
surface is limited and the area of gross pitting
appears to represent only a fraction of the total
surface. As is evident in Figure 3, the final CD I
was very high, < 23 mA, in comparison with
that recorded in Figure 4, < 10 mA at the same
concentration of 5 1021 M NaCl. This
indicates that in Figure 3, general dissolution
takes place, whereas in case of Figure 4,
initiation and propagation of pitting attack were
responsible for the dissolution of the Cu. By
decreasing the concentration of Cl2 to 102 1 M
(Figure 4), low frequency/high amplitude
fluctuations in current were observed after
about 90 min of immersion, confirming the
hypothesis that as the concentration of Cl2
decreased, the resistance of Cu2O passive film
increased.
During the fluctuation period, the CD
decreased to < 3 mA at the end of the run. This
decrease in current was due to the competition
between the initiation and repassivation, or the
blocking of pits with the corrosion products.
 Pitting corrosion of copper in chloride solutions Anti-Corrosion Methods and Materials
A. El Warraky, H.A. El Shayeb and E.M. Sherif Volume 51 Number 1 2004 5261

At 5 1022 M Cl2 ; fluctuations became very Figure 6 Current-time curves for copper in different concentrations of NaCl at
small (Figure 4), which was related to the 400 mV after immersion of the sample in oxygenated solution of 102 4 M NaCl
formation of very fine pits (i.e. micropits), that for 30 min pre-polarisation time
did not propagate, and the rate of repassivation
became higher than that which occurred at
higher concentrations (i.e. 102 1 and 5 1021 ).
At 102 2 M Cl2 , the recorded current became
very small and the fluctuations disappeared,
indicating in this case that the concentration of
Cl2 was insufficient to induce initiation of
pitting and the surface became completely
passive.
In earlier studies of pitting corrosion on pure
and low-alloyed copper (Duthil et al., 1996;
Qafsaoui et al., 1993; Mankowski et al., 1997), it
was reported that a linear relationship was
evident between the pit generation rate and the
chloride content. However, there is a critical
chloride content < 4:5 1022 M, below which
(i.e. at 3 1022 M Cl2 ) pit initiation is
observed, but the material always repassivates
before reaching the current threshold (102 4 A)
for detection.

3.2.2 In oxygenated NaCl

Several researchers (Ives and Rawson, 1962;
Hilbrun, 1983) proposed that, when copper is
immersed in an oxygenated aqueous solution, it
corrodes rapidly to form compact and adherent
film of cuprous oxide (Cu2O) which is in good
electrical contact with the underlying metal as:
Cu H2 O Cu2 O H e2 5

In the present investigation, oxygenation was

achieved by bubbling of oxygen gas for 30 min
in solution of 102 4 M NaCl before polarisation,
to allow the formation of a compact and
adherent film of Cu2O. Then, the same pre-
treated electrode was immersed in fresh solution
containing different concentrations of NaCl
1022 -5 1021 at a potential of 400 mV, at
which time the bubbling of oxygen was
interrupted. In case of freely aerated solutions
(Figure 6), the critical chloride concentration
was 5 1022 M Cl2 . At lower concentrations,
pitting corrosion did not occur. Another
observation was that all concentrations
5 1021 -5 1022 induced pitting (Figure 6),
where fluctuations in CD with time started from
the first moment of polarisation. The
fluctuation magnitude was larger, and the
frequency was small in comparison with that
58
recorded in case of freely aerated condition.
A higher value of net CD was recorded during
these tests, compared to the above values
obtained in the absence of oxygenation. In case
of 5 1021 M, a CD of 20 mA was obtained,
which was twice the value observed at the same
concentration in freely aerated solution. From
the above data, it can be concluded that
bubbling of oxygen not only affected the
formation of a compact and adherent film of
Cu2O, but also increased its thickness.
As can be observed in Figure 7(a), the
number of pits initiated under oxygenated
conditions was smaller than the number without
oxygenation (shown in Figure 5(a)), whereas
the number of pits which tended to propagate
was larger. This indicates that oxygenation
increased the oxide film thickness and this
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 7 SEM of copper in 5 1021 M NaCl at the end of
experiment of Figure 6 in two different areas. (a) Pitting area,
and (b) general surface condition
decreased the number of weak points where the
Cl2 ion could initiate attack. The area of the
weaknesses represented only a small fraction of
the total area, and was less than the case without
oxygen. Hence, pits occurred more rapidly in
the presence of oxygen than was the case in
deaerated conditions as a result of the increase
in cathodic activity, which causes an increase in
the degree of anodic activity. As the pitting
attack is concentrated at specific small points of
weakness in the oxide film, the fluctuations in
CD occurred with greater magnitude and
smaller frequency (Figure 6). On the other
hand, Figure 7(b) shows the majority of the
surface, indicating the presence of fewer
initiated pits compared to the area shown in
Figure 5(b).
Similar results were obtained in case of pre-
treatment of the electrode in 102 5 and 102 3,
both in freely aerated or oxygenated solutions.
At higher concentrations C $ 1022 M Cl2 in
the same conditions, the current-time curve did
not exhibit any fluctuations and the net CD
recorded was higher than that indicated earlier
in case of solutions of # 102 3 M NaCl. These
59
Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
results were confirmed by indications of general
dissolution of Cu at higher concentrations of
NaCl ($ 102 2), due to the formation of CuCl,
which is less protective than Cu2O.
4. Pitting corrosion mechanism
From the results of these studies, it was
concluded that pitting corrosion of copper
occurs when a protective film of Cu2O exists on
its surface in contact with higher concentration
of chloride solutions (102 2-5 1021 M NaCl).
From the above results, as shown in Figure 8,
the mechanism of pit formation develops in
different steps:
The first step (1) is the formation CuCl at all
concentrations of NaCl, as represented in
equation (2).
In the presence of dilute concentrations of
NaCl C # 1023 , the second step (2) becomes
possible, where CuCl may undergo hydrolysis,
as in equation (3), or due to the presence of
hydroxide ions, and Cu2O forms on the surface
as a result of cathodic reaction of oxygen
reduction (Bokris et al., 1981), i.e.:
2CuCl 2OH2 Cu2 O H2 O Cl2 6
The substitution of the chloride ions of the
CuCl film by oxygen ions leads to the formation
of a protective film of Cu2O as a result of
reactions (3) or (6). At the same time, there are
some small areas, which are covered with a very
thin layer of Cu2O over the trapped CuCl, as in
step (2). The chloride ion concentration
# 102 3 M is low, and cannot produce pitting,
but it may contribute to the formation of
Cu2O. After the formation of Cu2O in diluted
solution of NaCl, the solution was changed to
become more concentrated
(1022 ! 5 1021 M NaCl). At the pitting
potential (400 mV), step (3) in the mechanism
can be established, and the initiation of the pits
was found to occur at sites where CuCl was
trapped. The chloride can then dissolve, as
shown in equation (4), or can undergo the
disassociation reaction:
2CuCl CuCl2 Cu 7
This latter reaction was proposed (El Warraky,
1997; Mankowski et al., 1997; Xia and
 Pitting corrosion of copper in chloride solutions
A. El Warraky, H.A. El Shayeb and E.M. Sherif
Figure 8 Schematic representation of the mechanism of pitting corrosion of copper in NaCl solutions
Smialowska, 1990) but did not appear to occur
in the investigation, or was present only as a very
small proportion of activity that was below the
detection limit of the XPS analysis unit, where
the Cu and CuCl2 peaks are not recorded.
The main dissolution reaction occurred
through the formation of a CuCl2-soluble
complex at specific sites, leading to the
formation of micro-pits in the initial stage of
pitting. The number of initiated and the
propagated pits depends on steps (5) and (6)
during increasing concentrations of NaCl.
From the above, it was concluded that
chloride ions were the species primarily
responsible for causing pitting of copper at
higher chloride concentrations (102 2-
5 1021 M, though the presence of a
protective film of Cu2O also was important in
causing the pitting condition.
5. Conclusions
(1) In dilute solutions of NaCl C # 1023 M,
XPS analysis showed that the predominant
species in the surface film was Cu2O, but as
the concentration of NaCl was increased
the surface film was mainly CuCl.
Potentiostatic polarisation tests alone were
not capable of providing precise
information about the pitting corrosion
behaviour of Cu in NaCl solution.
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Anti-Corrosion Methods and Materials
Volume 51 Number 1 2004 5261
(2) CuCl is less protective than Cu2O and
dissolving copper ions pass through the
CuCl2 2 soluble complex. Dissolution is not
due to the formation of soluble CuCl2.
(3) Pitting of copper occurs when a protective
film of Cu2O exists on its surface in
contact with concentrated solution of NaCl
(102 2-5 1021 M:
(4) Chloride ions act in the formation of Cu2O
and are the ions responsible for the
initiation of pitting attack.
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