Corrosion Science 47 (2005) 1370–1383

www.elsevier.com/locate/corsci

Atmospheric corrosion of copper under

wet/dry cyclic conditions
Gamal A. EL-Mahdy *

Department of Metallurgical System Engineering, Yonsei University, 134-Shinchon-dong,

Seodaemun-Ku, Seoul, 120-749, South Korea

Received 3 June 2003; accepted 21 July 2004

Available online 14 October 2004

Abstract

The polarization resistance of copper subjected to NaCl and an ammonium sulfate solution
under wet/dry cycling conditions was monitored using an EIS impedance technique. The cop-
per samples were exposed to 1 h of immersion using different solutions of pH, temperature and
surface orientation and 7 h of drying. The copper plates corroded more substantially on the
skyward side than those for a ground ward side. The degree of protection copper oxide provides
decrease in an acidic medium (pH 4) more than in a neutral medium (pH 7). The corrosion rate
of copper increases rapidly during the initial stages of exposure then decreases slowly and even-
tually attains the steady state during the last stages of exposure. The corrosion products were
analyzed using X-ray diffraction. The corrosion mechanism for copper studied under wet/dry
cyclic conditions was found to proceed under the dissolution–precipitation mechanism.

2004 Elsevier Ltd. All rights reserved.

Keywords: Copper; EIS; Atmospheric corrosion; XRD

1. Introduction

The atmospheric corrosion of copper and its alloys has become a subject of great
interest due to numerous applications in related structural, architectural, electrical

*
Permanent address: Chemistry Department, Faculty of Science, Helwan University, Ain-Helwan,
Cairo, Egypt.

0010-938X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.07.034
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1371

and electronics usage. The effect of NaCl in combination with O3 on the atmospheric
corrosion of copper was investigated [1]. The corrosion products formed after four
weeks of exposure were characterized qualitatively by using X-ray diffraction and
quantitatively evaluated by gravimetric and ion chromatography measurements of
the leaching solution. The corrosive effect of NaCl was strong in purely humid air
and in air containing O3 or SO2. The corrosion rate was proportional to the amount
of chloride added and increased along with relative humidity. The corrosion of cop-
per studied under various chloride conditions [2–5] resulted generally in reaction
products such as cuprous, cupric oxides, cuprous hydroxide and cuprous chloride.
Recently Chimielova et al. [6] identified the corrosion products precipitated on cop-
per surface after four days treatment in sodium chloride, sodium/magnesium and
sodium/calcium chloride solutions while using a X-ray diffraction powder analysis.
The corrosion products identified were Cu2(OH)3Cl, Cu2O and CuCl2.
The effect of submicron (NH4)2SO4 particles on the atmospheric corrosion of cop-
per was investigated at varying relative humidities and temperatures (300 and 373 K)
[7–9]. Laboratory simulations have shown that (NH4)2SO4 particles led to the corro-
sion products found in natural patinas.
Corrosion under condensed water and cyclic wet and dry conditions pose signif-
icant problems for many applications, such as building and bridges, which are
strongly dependent on the duration and conditions of daily dry and wet cycles.
The presence of NaCl in a marine environment has a strong corrosive effect toward
copper under thin electrolyte layers and in alternating wet/dry cyclic conditions. The
application of conventional electrochemical techniques used for monitoring the
atmospheric corrosion of metals is quite difficult due to the presence of thin electro-
lyte layers created during the drying process. A high solution resistance and a non-
uniform current distribution over the working electrode are the main limitations
observed for the inapplicability. It has been established that AC impedance technique
was successively applied to monitor the corrosion rate of the steel [10,11], coated
steel [12,13] and metals [14–16] under wet/dry cyclic conditions and with thin electro-
lyte layers. In all of these studies, a two-electrode cell configuration was employed.
There have no been studies conducted on the atmospheric corrosion of copper
under wet/dry cyclic conditions. The aim of the work is to monitor the corrosion rate
of copper during cyclic wet/dry conditions and in a chloride containing environment
together with the variations of surface orientation, temperature and pH of solution.
The work will also extend to investigate the effects of an ammonium sulfate solution
as well as to suggest a mechanism for copper corrosion experienced under wet/dry
cyclic conditions.

2. Experimental procedure

2.1. Material and electrode preparation

Two-electrode cell configuration were fabricated from copper sheet (99.99) 10 mm

(width) · 10 mm (length) and embedded parallel in an epoxy resin with 0.1 mm
1372 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

40 mm

0.5 mm
Peripheral bank

0.1mm Electrodes
10 mm

0.5 mm

10 mm

Wire for
Epoxy
Electrodes connection

Top View Transverse cross-sectional View

Fig. 1. Schematic diagram of the cell used in an AC impedance monitoring experiment conducted under
wet/dry cyclic conditions.

separation as shown in Fig. 1. The electrode was polished on SiC-paper in ethanol to

1000 mesh, then washed in ethanol using an ultrasonic agitation. The sample was put
in a desiccator until the start of the exposure process.

2.2. Atmospheric exposure

The cell containing the two electrodes was fixed horizontally on an acrylic vessel
with dimensions of 8 cm · 8 cm · 8 cm with the aid of a water leveler. In all exper-
iments, the cell was placed with the metal surface facing upwards except for the
specimen, which was oriented in a downward direction and placed inside a temper-
ature–humidity controlled chamber. The cell was subjected to 1 h of immersion in
NaCl or ammonium sulfate solution. The test solution was introduced from an exter-
nal tank through an inflow magnetic valve programmed to deliver a pre-determined
volume used to cover the test specimen. The solution was drained through an out-
flow magnetic valve after 1 h of immersion and the solution on the surface was left
to dry for 7 h at 60% RH and 303 K. The volume of the electrolyte used during
immersion period was the same in all experiments (1 h of immersion). Both the in-
flow and the outflow magnetic valves were controlled by using a cyclic on–off timer
control. The wet/dry cycles were conducted for a total period of 96 h. To ensure the
constancy of electrolyte layer thickness at the onset of each dry cycle, a peripheral
bank whose thickness is 0.5 mm (Mylar sheet) was fixed on top of the electrode sur-
face as shown in Fig. 1. This provides an initial thickness of the electrolyte layer of
about 0.5 mm in all experiments remained during the drying process except for the
specimen oriented in the downward direction, because there is no electrolyte re-
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1373

mained over the specimen during drying owing to the surface orientation. The only
wetting period the specimen experiences is the first hour of immersion during expo-
sure of the downward oriented specimen.

2.3. Monitoring of the polarization resistance

The impedance measurement was conducted at 10 kHz (ZH) and 10 mHz (ZL)
using a Solartron 1280, which was controlled by using a computer through GPIB
interface. The polarization resistance Rp was determined by subtracting the high fre-
quency impedance measured at 10 kHz (ZH) from the low frequency impedance
measured at 10 mHz (ZL). Two-electrode cell configuration was used for monitoring
the polarization resistance. The reciprocal value of the polarization resistance was
proportional to the corrosion rate [10–16].

2.4. Material characterization

The corrosion products were analyzed by using a Shimadzu (Japan) XD-3A dif-
fractometer measured with CuKa monochromatic radiation (k = 1.5405 Å). The
measurement was conducted in a step scanning mode (2/min) from h = 30 to
h = 80. X-ray diffraction data was taken directly from the surface of the copper after
exposure for 96 h under wet/dry cyclic conditions.

3. Results and discussions

3.1. Exposure at different surface orientation

The polarization resistance (Rp) was monitored under 1 h of immersion and 7 h of

drying in 0.01 M NaCl solution at 60% RH and 303 K temperature for samples ex-
posed to both skyward and downward directions. The corrosion rate is proportional
to the reciprocal of polarization resistance and can be calculated using the Stern–
Geary equation [17]:

Corrosion rate ¼ K=Rp ; ð1Þ

K ¼ ðba
bc Þ=2:303ðba þ bc Þ; ð2Þ

where ba and bc represent anodic and cathodic Tafel slope, respectively. The value of
K is a function of metal and electrolyte [12,15] and can be assumed to be constant for
a given metal/electrolyte system.
Therefore, the average of the reciprocal of polarization resistance per cycle
(ARPR) was evaluated to represent the average corrosion rate per cycle and calcu-
lated from 1/Rp according to the following equation:
1374 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

Average of reciprocal of polarization resistance per cycle ðARPRÞ

Z t
¼ 1=Rp dt; ð3Þ
0

where t is the time of wetness (TOW) per cycle and 1/Rp is the reciprocal polarization
resistance. The time of wetness (TOW), which can be estimated from using the 1/Rp
data versus exposure time as the total elapsed time, from the wetting period to the
time just before the completion of surface drying (1/Rp dropped to a value of zero
during complete drying of surface).
Fig. 2 shows that the reciprocal of polarization resistance (1/Rp) which is propor-
tional to the corrosion rate [10–16], increases with the immersion time during the ini-
tial stage then attains a steady state during the last stage of exposure. Fig. 3 shows
that ARPR, of the skyward-oriented sample is higher than those for a downward-
oriented sample. The ARPR of the skyward-oriented sample, increases gradually
and reaches its maximum during the eighth cycle then attained a steady state during
the subsequent four cycles. In the case of downward-oriented sample, the ARPR in-
creases slowly and reaches its maximum during the third cycle and attains a steady

0.00018

0.00015 Facing downward

0.00012

0.00009

0.00006

0.00003
1/Rp, Ω-1 cm-2

0.00000
0.00018

Facing upward
0.00015

0.00012

0.00009

0.00006

0.00003

0.00000
0 24 48 72 96
Exposure time (hour)

Fig. 2. Changes of 1/Rp with exposure time of a copper sample facing in both a downward and upward
direction measured under wet/dry cyclic conditions in 0.01 M NaCl solution.
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1375

Average of Reciprocal of Polarization Resistance

0.0030

0.0025 upward
downward

per cycle (ARPR), Ω-1 cm-2

0.0020

0.0015

0.0010

0.0005

0.0000
0 2 4 6 8 10 12 14 16
Exposure wet/dry cycle

Fig. 3. Variation of average corrosion charge with cycle number of the copper sample facing downward
and upward direction.

state during the subsequent six cycles. This result can be attributed to the difference
in the time of wetness (tTOW) which is 4 and 1 h per cycle for both skyward and
downward sample, respectively. The amount of electrolyte retained on the surface
of the skyward sample during the drying process stimulates the corrosion process
occurring under thin electrolyte layers. The electrolyte evaporates and concentrates
during thinning process leading to a shorter path for oxygen diffusion, which is the
rate-determining step in the corrosion process under thin electrolyte layers. In the
groundward sample the corrosion process occurs only during the immersion period
of each cycle. The surface is passivated and lowers the corrosion process during the
subsequent cycles. One part of the corrosion products was washed away from the
surface during the next cycle and the other retained it. The steady state observed dur-
ing the last stages of copper corrosion under wet/dry cycling conditions was attrib-
uted to the entire covering of the surface with corrosion products, which inhibits the
continuity of the corrosion process. X-ray diffraction indicated the presence of Cu2O,
Cu2(OH)3Cl and Cu2Cl as corrosion products. The main constituent corrosion prod-
uct in case of groundward sample is Cu2O.

3.2. Influence of temperature

The effect of temperature was investigated in 0.05 M NaCl solution at two differ-
ent temperatures (293 and 313 K) at 60% RH under 1 h of immersion time and dur-
ing 7 h of drying as shown in Fig. 4. The sample exposed was facing upward during
all investigations. The reciprocal of polarization resistance at 313 K is higher than
that at 293 K. The 1/Rp increases with exposure time then decreases during the last
stages at both temperatures. The calculated ARPR vs. cycle number is presented in
Fig. 5. The differences in behavior at high and low temperature may be attributed to
the formation of more protective corrosion products at low temperature. The results
1376 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

0.0030

T = 293 K
0.0025

0.0020

0.0015

0.0010

0.0005
1/Rp, Ω-1 cm-2

0.0000
0.0030
T = 313 K
0.0025

0.0020

0.0015

0.0010

0.0005

0.0000
0 24 48 72 96
Exposure time (hour)

Fig. 4. Monitoring results of 1/Rp vs. exposure time for copper measured under wet/dry cyclic conditions
in a 0.05 M NaCl at 60% RH, and at two different temperatures.
Average of Reciprocal of Polarization Resistance

0.040

0.035 T = 313 K
T = 293 K
per cycle (ARPR), Ω-1 cm-2

0.030

0.025

0.020

0.015

0.010

0.005

0.000
0 2 4 6 8 10 12
Exposure wet / dry cycle

Fig. 5. Influence of temperature on the average corrosion charge of copper in a 0.05 M NaCl solution.

may be explained on the basis of diffusion process of oxygen, which was enhanced at
a higher temperature during the drying process under thin electrolyte layers when
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1377

observed with the rising of temperature, while the reduction of oxygen is a rate-deter-
mining step in the corrosion process under thin electrolyte. Hence, the corrosion rate
of copper increases with an increase in temperature. In addition, the dissolution of
the protective oxide followed by copper metal loss is enhanced by an increase in tem-
perature during the immersion period (anodically control in bulk solution) which
leads to an increase in the observed corrosion rate. The cuprite formed at the lower
temperature was more protective than that measured at 313 K. It seems that the
property of cuprite changed to become less protective during exposure experienced
at high temperature. Thus creating a greater tendency for ion diffusion into the cor-
rosion layer. NaCl causes a breakdown of the passive film (mainly cuprite) due to the
formation of soluble species such as CuCl2. The average reciprocal of polarization
resistance observed at both temperature increases and together with the cycle num-
ber, reaches its maximum during the third cycle and attains a steady state during the
last seven cycles with different steady state values. The compounds Cu2O and
Cu2(OH)3Cl and Cu2Cl were identified as corrosion products by using X-ray
diffraction.
It is clear that the ARPR presented in Fig. 3 (0.01 M NaCl) increases gradually as
the exposure cycle increases then eventually attains the steady state during the ninth
cycle. However, in Fig. 5 (0.05 M NaCl) ARPR increases rapidly to a maximum
value in the third cycle then decreases slowly until reaches its steady state during
the subsequent sixth cycle. The difference in corrosion behavior can be attributed
to the difference in the amount of corrosion products precipitated over the entire
copper surface. In Fig. 3, while the concentration is lower than in Fig. 5, the corro-
sion rate proceeds slowly and the amount of corrosion products partially covered the
copper surface until it reaches a steady state during the ninth cycle, while the surface
is entirely covered with corrosion products. In Fig. 5 the corrosion rate increases rap-
idly due to a higher concentration of NaCl which leads to an increase in the amount
of corrosion products until it attains a maximum in the third cycle. The observed de-
crease in the corrosion rate measured during fourth and fifth cycles can be attributed
to the dissolution process of some precipitated corrosion products, which are loosely
bound to the copper surface. The ARPR reaches its steady state during the sixth
cycle due to the entire covering of the surface with the reformation of corrosion
products. It can be concluded that the higher the concentration of NaCl, the faster
the steady state occurs due to the larger amount of corrosion products precipitated
over the copper surface.

3.3. Exposure at different pH

To study the influence of pH on the atmospheric corrosion of copper, two exper-

iments were conducted in 0.025 M NaCl solution. The copper was subjected to 1 h of
immersion and 7 h of drying at 298 K and 60% RH. Both samples were exposed fac-
ing upward. The data depicted in Fig. 6 indicated that the overall amount of copper
corrosion increases with the lowering of the solution pH. The ARPR per cycle was
calculated and presented in Fig. 7. The values of ARPR, at low pH are higher than
those at pH 7. The results imply that pH is an important parameter to be considered
1378 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

0.00040
pH = 7
0.00032

0.00024

0.00016

0.00008
1/Rp, Ω-1 cm-2

0.00000
0.00040

pH = 4
0.00032

0.00024

0.00016

0.00008

0.00000
0 24 48 72 96
Exposure time (hour)

Fig. 6. Variation of 1/Rp with exposure time for copper subjected to 0.025 M NaCl at two different pH
solutions under wet/dry cyclic conditions.
Average of Reciprocal of Polarization Resistance

0.0040

0.0035
pH = 4
per cycle (ARPR), Ω-1 cm-2

0.0030 pH = 7

0.0025

0.0020

0.0015

0.0010

0.0005

0.0000
0 2 4 6 8 10 12 14 16
Exposure wet / dry cycle

Fig. 7. Variation of average corrosion charge with exposure cycle number measured at two different pH
solutions.
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1379

for Cu corrosion under wet/dry cycling conditions. Hydrogen ions can promote Cu
corrosion as described in the equation below:
2Cu þ 4Hþ þ O2 ¼ 2Cu2þ þ 2H2 O ð4Þ
At pH 7 a possible passivation process on the copper surface may decrease the cor-
rosion rate.
The morphology of the deposited corrosion products was distributed heterogene-
ously, showing some paths through which copper ions released and chloride ions dif-
fused. The corrosion rates of copper exposed to acidic chloride solution are initially
higher than those observed in the neutral solution and decrease with increasing expo-
sure cycles. The ions of Cu(I) are oxidized by atmospheric oxygen into Cu(II) and
the latter ion plays an important role in copper corrosion. Through hydrolysis of
the Cu(II) ions, basic copper chloride is formed in a neutral medium (paratacamite)
4Cu2þ þ 2Cl þ 6H2 O ¼ Cu4 Cl2 ðOHÞ6 þ 6OH ð5Þ
The main corrosion products identified by using XRD-data after 96 h exposure was
cuprite, paratacamite, and clinoatacamite (Cu2(OH)3Cl) in neutral and natokite
(CuCl) in acidic solution. Copper surface formed a protective passive film of cuprite
in the neutral medium [18,19], however in the acidic medium cuprite was not stable.

3.4. Corrosion behavior of copper in ammonium sulfate solution

The polarization resistance was conducted with exposure time in 0.05 M ammo-
nium sulfate solution, under wet/dry cyclic conditions at 303 K and 60% RH as
shown in Fig. 8. The surface of copper was exposed facing upward. The ARPR val-
ues were calculated using Eq. (1) and traced versus the cycle number as displayed in
Fig. 9. The ARPR increases during the initial stages due to the dissolution of copper
as Cu(NH3)2+ and attains its maximum value during the third cycle. The ARPR

0.0020

0.0015
1/Rp, Ω-1 cm-2

0.0010

0.0005

0.0000
0 24 48 72 96
Exposure time (hour)

Fig. 8. Changes in the 1/Rp with time for copper exposed to alternating conditions, of wet/dry cyclic
conditions and in a 0.05 M ammonium sulfate solution at 303 K and 60% RH.
1380 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

Average of Reciprocal of Polarization Resistance

0.040

0.035

0.030

per cycle (ARPR), Ω-1 cm-2

0.025

0.020

0.015

0.010

0.005

0.000
0 2 4 6 8 10 12 14 16
Exposure wet/dry cycle

Fig. 9. Plots of the average corrosion charge for copper with exposure cycle number and in an ammonium
sulfate solution conducted at 303 K and 60% RH.

starts to decrease slowly reaching a steady state during the subsequent five cycles.
Cuprite is the major corrosion product formed in the early stages of atmospheric cor-
rosion of copper occurring in a natural environment. The basic copper sulfate Cu3-
(SO4)(OH)4 (antertlerite) and Cu4(SO4)(OH)6 (bronchatite) compounds formed
during the latter stages of corrosion as revealed from X-ray diffraction analysis.
Fig. 10 represents the magnified plot of the second cycle displayed in Fig. 9 and
can be divided into three distinct regions. Experimentation indicates that the corro-
sion rate is high during the onset of region I (1 h of immersion) due to dissolution of
the precipitated ammonium sulfate formed in the preceding cycle and during the dry-
ing process of the first cycle, leading to an increase in the concentration of ammo-
nium sulfate, which results in an increase in the corrosion rate in region I. The

0.0036

0.0030

Time of wetness
0.0024
1/Rp, Ω-1 cm-2

I II III

0.0018
Onset of drying period

Complete dryness of surface

1-hr immersion

0.0012

0.0006

0.0000
8 9 10 11 12 13 14 15 16
Exposure time (hour)

Fig. 10. Monitoring results for a single wet/dry cycle (second cycle in Fig. 9) showing the variations of
1/Rp versus the exposure time.
 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383 1381

observed decrease in the corrosion rate within the region I was attributed to the pass-
ivation of the copper surface with corrosion products. The overall corrosion rate in-
creases gradually as the drying time progresses in region II due to an increase in the
ammonium sulfate concentration as a result of electrolyte evaporation. In addition,
the diffusion of oxygen increases as the thickness of electrolyte decreases as the dry-
ing time increases, leading to an increase in the corrosion rate under thin electrolyte
layers. The sharp decrease in the corrosion rate during the end of region II was
attributed to the complete drying of the surface and 1/Rp dropped to a value of zero.
There was no corrosion process during region III as a result of complete the dryness
of the surface. Fig. 10 shows an estimation of the time of wetness (TOW), measured
from 1/Rp data versus exposure time as the total elapsed time, from the wetting per-
iod (region I) to the time just before the complete surface drying period and at the
end of region II.

3.5. Mechanism of copper corrosion

The mechanism of copper corrosion experienced under wet/dry cyclic conditions

seems to proceed under the dissolution–precipitation mechanism. The first step is the
dissolution process of the air-formed oxide film followed by the dissolution of copper
leads to a high corrosion rate observed during the initial stages of exposure. The dis-
solution process proceeds under a wet period (1 h of immersion) and continues under
the thin electrolyte layers, and during drying period. The dissolution process in-
creases at high temperature and low pH due to the enhancement of the diffusion
process of chloride ions, which causes a breakdown of the film formed on the copper
surface. The breakdown of the film is also enhanced at low pH = 4 due to the disso-
lution of the passive film and formation of copper (1) chloride, which is described as
follows:

1=2Cu2 O þ 2Cl þ Hþ ! CuCl2 þ 1=2H2 O ð6Þ

A small fraction of the corrosion products is retained on the copper surface during
the initial exposure. During the immersion period, one part of the corrosion products
formed on freely exposed copper will remain on the surface whereas another part will
be released and washed off. The degree of protection depends on the stability of the
formed corrosion products. During the last stages of exposure the amount of corro-
sion products and the degree of protection increases concurrently with exposure time
due to the precipitation of thick corrosion products. Hence, the corrosion rates de-
crease and approach a steady state value. Decreasing the corrosion rates along with
exposure time was attributed to the continuous build up of protective corrosion
products on the copper surface.
In an ammonium sulfate solution, the rate of corrosion is high during the initial
stages, then decreases slowly and attains a steady state during the last stages of expo-
sure. The corrosion rate increases during the initial stages of exposure due to the for-
mation CuðNH3 Þþ 2 then decreases during the final stages of corrosion, due to the
formation of insoluble basic copper sulfate, antlerite, brochantite and posnjakite.
1382 G.A. EL-Mahdy / Corrosion Science 47 (2005) 1370–1383

The cathodic reaction occurring during the atmospheric corrosion of copper is the
reduction of oxygen:
O2 þ 2H2 O þ 4e ¼ 4OH ð7Þ

4. Conclusions

From the results observed during monitoring the polarization resistance of copper
under wet/dry cyclic conditions, in chloride and ammonium sulfate containing envi-
ronments, the following conclusions were drawn:

1. The application of AC impedance and the experimental set up used in this inves-
tigation have proven to be a successful tool as well as a useful arrangement when
used for monitoring the atmospheric corrosion of copper under periodic wet/dry
conditions.
2. The presence of the thin electrolyte layers during the drying period enhances the
corrosion process of copper in the upward-oriented sample and the corrosion
rates are higher than those of downward-oriented specimen.
3. Exposure of copper tested in a marine environment indicated that NaCl has a
strong effect on copper corrosion. The mechanism of atmospheric corrosion of
copper under wet/dry cyclic conditions proceeds under dissolution–precipitation
mechanism. The corrosion rate of copper increases rapidly during the initial
stages of exposure then decreases slowly and eventually attains a steady state dur-
ing the last stages of exposure.
4. The inhibitive action of copper-oxide decreased more gradually in an acidic med-
ium (pH 4) than in a neutral medium.

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