Corrosion Science 50 (2008) 3168–3178

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Influence of pH and chloride ion concentration on the corrosion of Mg alloy ZE41

Ming-Chun Zhao a,b,c, Ming Liu a,b, Guang-Ling Song a, Andrej Atrens a,b,*
a
Division of Materials, The University of Queensland, Brisbane, Qld 4072, Australia
b
Swiss Federal Laboratories for Materials Science and Technology, EMPA, Department 136, Überlandstrasse 129, CH-8600 Dubendorf, Switzerland
c
School of Material Science and Engineering, Central South University, Changsha 410083, PR China

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

Article history: The influence of pH and chloride ion concentration on the corrosion behaviour of ZE41 was studied using
Received 4 June 2008 immersion tests and electrochemical measurements. A shorter incubation period to the onset of corro-
Accepted 14 August 2008 sion; a more negative corrosion potential; and a higher corrosion rate correlated with a higher chloride
Available online 26 August 2008
ion concentration at each pH value and correlated with a lower pH value for each chloride ion concentra-
tion. This corrosion behaviour is consistent with the current understanding that the corrosion behaviour
Keywords: of magnesium alloys is governed by a partially protective surface film, with the corrosion reactions occur-
Mg alloy ZE41
ring predominantly at the breaks or imperfections of the partially protective film. The implication is that
Corrosion
pH
the fraction of film free surface increases with decreasing bulk pH and with increasing chloride ion con-
Chloride ion concentration centration. This is consistent with the known tendency of chloride ions to cause film breakdown and the
Surface film known instability of Mg(OH)2 in solutions with pH less than 10.5. The electrochemical measurements of
the corrosion rate, based on the corrosion current at the free corrosion potential, did not agree with direct
measurements evaluated from the evolved hydrogen, in agreement with other observations for Mg.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction protective; as a result the corrosion rate is typically more than

Mg alloys are of great interest in transport applications, espe-
cially for automobiles, due to their low density and adequate
strength/weight ratio. However, a critical limitation for the service
application of Mg alloys is their susceptibility to corrosion [1–3]
and hence there continues to be much research to understand
and document the various aspects of the corrosion of Mg alloys
[4–33]. Stress corrosion cracking (SCC) of common Mg alloys oc-
curs for frequently encountered environments [34–43] so SCC
may occur for stressed auto components subjected to road splash;
the fact that SCC of common Mg alloys occurs in distilled water
[34–39] indicates that water itself is the key environment factor
causing SCC in aqueous solutions.
The key points of the generally accepted corrosion mechanism
for Mg alloys [1–3] in common environments like 3% NaCl solution
are as follows. A partially protective film covers the surface and
corrosion occurs at the breaks in this film (i.e. at film free areas).
The cathodic reaction is hydrogen liberation. A step in the anodic
reaction is the production of the uni-positive Mg ion, Mg+, and a
fraction undergoes chemical reaction with water to liberate hydro-
gen [1–3]; thus, hydrogen is produced both chemically and as the
cathodic partial reaction. The surface film on Mg is not particularly
* Corresponding author. Address: Division of Materials, The University of
Queensland, Brisbane, Qld 4072, Australia. Tel.: +61 7 3365 3748; fax: +61 7 3365
3888.
E-mail address: andrejs.atrens@uq.edu.au (A. Atrens).
1 mm/y in common environments like 3% NaCl solution; no alloy-
ing element has been found that produces a solid solution Mg alloy
with a corrosion rate less than that of pure Mg in 3% NaCl solution
(which typically has a corrosion rate of 1 mm/y). Consequently, it
is useful to include pure Mg as a standard in any comparative study
of corrosion performance of Mg alloys (see e.g. [2,7,8,45]). More-
over, it is indeed extremely important to use pure Mg as the stan-
dard for comparison; commercial purity Mg can have a corrosion
rate more than 50 times that of pure Mg [2] and so ‘‘commercial
purity Mg” should be designated as ‘‘low purity Mg” for clarity.
Corrosion of common commercial Mg alloys typically involves
microgalvanic acceleration of the corrosion of the alpha matrix
by the second phase(s) [2,7,8,44,45] and corrosion rates are equal
to or typically greater than that of pure Mg. The corrosion rate of
a two phase Mg alloy can, however, be lower than that of pure
Mg for an appropriate distribution of the second phase in the alloy
(or at least at the alloy surface) [2,25,44]: namely, if the second
phase is finely divided, essentially continuous and the second
phase itself has a lower corrosion rate than that of pure Mg, then
the second phase can act as a corrosion barrier.
The corrosion form of magnesium is typically designated as
localised corrosion [1,2,48,49] to distinguish it from the auto-cata-
lytic pitting in stainless steels. Localised corrosion in magnesium
typically initiates as irregular localised corrosion, which spread
laterally and cover the whole surface. There does not seem to be
much tendency for deep pitting. The most probable reason is that

0010-938X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.08.023
 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178
the cathodic reaction is the liberation of hydrogen. A by product of
that cathodic reaction is the production of OH ions (or equiva-
lently the consumption of H+ ions) with a concomitant increase
of the pH and stabilisation of the local magnesium hydroxide film
and a decrease in corrosion tendency. Thus localised corrosion in
magnesium has an inherent tendency to be self-limiting. This is
in marked contrast to the situation for stainless steels, where the
occluded pit cell becomes more aggressive and accelerates the
localised corrosion.
Corrosion of magnesium has a number of seemingly strange
phenomena. The best known may be the negative difference effect,
commonly referred to as NDE [2–5]: the amount of hydrogen liber-
ated increases with increasing applied anodic current (that de-
creases the cathodic reaction rate and the amount of associated
‘‘cathodic” hydrogen) and the amount of magnesium dissolved is
greater than expected from application of the Faraday Law; both
effects are explained by the generally accepted Mg corrosion
mechanism involving the uni-positive Mg ion, Mg+. Another well
know effect is that electrochemical measurements of the corrosion
rate, based on the corrosion current at the free corrosion potential,
do not agree with direct measurements using weight loss or eval-
uated from the evolved hydrogen [2,10,46,47].
Much of the mechanistic understanding of the magnesium cor-
rosion mechanism [1–3] has been gained in studies [44,48–50]
using pure Mg and Mg–Al alloys. Are the same issues involved in
the corrosion of other Mg alloy systems? To answer this question,
we picked ZE41, a commercial alloy, and we are carrying out a sys-
tematic investigation of the corrosion behaviour of ZE41. In a re-
cent paper, Aghion et al. [51] indicates that ZE41 is still preferred
for certain applications although it exhibits poor corrosion resis-
tance. ZE41 was used for the gear case of the French Freron
super-helicopter [52] and for the wheels of the champion racing
car in the years of 1990 and 1991 [53]. ZE41 has the nominal com-
position Mg-4 wt% Zn-1 wt% RE. Its microstructure, as-cast, typi-
cally consists of an a-phase matrix and b-phase distributed along
the a-phase grain boundaries [8,54]. There has been a significant
amount of research over the last few years exploring the corrosion
behaviour of Mg–Zn and Mg–RE alloys [55–62], which give valu-
able insights into the corrosion behaviour of ZE41.
Our prior paper [8] reported on the influence of microstructure
on the corrosion of as-cast ZE41 in 1 M NaCl. The corrosion rate of
ZE41 was approximately double that of AZ91 and about thirteen
times that of pure Mg. The second phase in ZE41 did not act as a
corrosion barrier and did not stop the advance of corrosion. As a
consequence, the alpha Mg matrix corroded over the whole surface
with little or no corrosion of the second phase. The mechanism of
microgalvanic acceleration of corrosion for ZE41 was the same as
for the Mg–Al alloys.
Mg alloys in auto service may encounter environments, partic-
ularly aqueous solutions from road splash, with different pH values
and chloride ion concentrations. Are there any qualitative differ-
ences in their corrosion behaviour in these different environ-
ments? The influence of pH, chlorides and sulphates on the
corrosion and electrochemical behaviour of pure magnesium was
studied by Song et al. [48,49]; the corrosion and electrochemical
behaviour of pure magnesium, AZ21, AZ501 and AZ91 in sodium
chloride solutions was studied by Song et al. [49,50]; the influence
of pH and chloride ion concentration on the corrosion and electro-
chemical behaviour of AZ91D was then further studied by Ambat
Table 1
Chemical composition of ZE41 (wt%)
Zn Ce La Pr Mn Fe Al Be
4.59 1.05 0.48 0.12 0.02 0.006 0.004 <0.001
3169
et al. [63] and of cast AZ63 by Altun et al. [64]. To date, however,
there has been no detailed study on the effect of pH value and chlo-
ride ion concentration on the corrosion behaviour of ZE41, nor in
the Mg–Zn and Mg–RE alloys [55–62], which give valuable insights
into the corrosion behaviour of ZE41. From a practical view point,
understanding on the influence of pH and chloride ion concentra-
tion on the corrosion behaviour of ZE41 is of significance and is
essential for the understanding of environmental factors control-
ling ZE41 corrosion.
This work investigated these aspects for ZE41 using immersion
corrosion tests and by evaluating the electrochemistry of ZE41. The
aim was to determine if there were any qualitative differences in
the corrosion behaviour of ZE41 in these different environments
or if the corrosion behaviour is consistent with the current under-
standing of the corrosion mechanism of magnesium alloys [1–3].
The electrochemical measurements were included to explore the
relationship, if any, between that electrochemical measurements
of the corrosion rate, based on the corrosion current at the free cor-
rosion potential, and direct measurements using weight loss or
evaluated from the evolved hydrogen, because of the known
[2,10,46,47] issue that electrochemical measurements of the corro-
sion rate, based on the corrosion current at the free corrosion po-
tential, do not agree with direct measurements using weight loss
or evaluated from the evolved hydrogen.
2. Experimental procedure
ZE41 specimens were cut from an as-cast ingot; the chemical
composition is presented in Table 1. The microstructure was exam-
ined in the un-etched condition by optical microscopy and scan-
ning electron microscopy (SEM) after metallographic preparation
(mechanical grinding successively to 1200 grit SiC paper, polishing
to 0.5lm diamond, washing with distilled water and drying with
warm flowing air).
The corrosion behaviour was characterized by immersion tests
at room temperature in 0 M, 0.1 M and 1 M NaCl solutions; the
pH of the solutions was adjusted to the desired value (3, 7 and
11) with HCl and NaOH. Solutions were made with analytical grade
reagents and distilled water. The solutions designated as 0 M NaCl
consisted of distilled water + zero NaCl, adjusted to the desired pH
value with HCl and NaOH. The aim was to investigate the corrosion
behaviour of ZE41 in acid, neutral and alkaline solutions that might
be encountered in auto service. The samples for the corrosion eval-
uation (including hydrogen gas collection and potentiodynamic
polarisation curves) were mechanically ground to 1200 grit SiC pa-
per, washed with distilled water and dried with warm flowing air.
Corrosion macro-morphology was examined using optical micros-
copy after immersion. Samples for hydrogen gas collection, to char-
acterise the corrosion rate during solution immersion, were cut
into coupons and encapsulated into epoxy resin so that a surface
with the dimension of 18 mm  27 mm was horizontally im-
mersed in 1500 ml of quiescent test solution, in a beaker open to
laboratory air. The hydrogen evolved during the corrosion experi-
ment was collected in a burette above the corroding sample. The
overall magnesium corrosion reaction,
Mg þ Hþ þ H2 O ¼ Mg2þ þ OH þ H2 ð1Þ
indicates that one molecule of hydrogen is evolved for each atom of
corroded magnesium.
Sn Pb Ni Cr Cu Zr Sr Nd Mg
<0.002 <0.002 <0.001 <0.001 <0.002 <0.002 <0.001 <0.01 Balance
3170 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178

Potentiodynamic polarisation curves were measured immedi-

ately after immersion of the specimen in the solution in a glass
cell using a PAR-2263 potentiostat system at a scan rate of
0.2 mV/s. In addition some potentiodynamic polarisation curves
were measured, using a procedure similar to that described above,
after the sample had been immersed for 48 h in the solution
(0.1 M NaCl, pH 3 and 11 and 1 M NaCl,pH 3 and 7) and steady
state corrosion conditions had become established. The polarisa-
tion curves were started by stepping the potential several hun-
dred mV negative to the steady state potential and then
polarising in an anodic direction at a scan rate of 0.2 mV/s. Sam-
ples for the potentiodynamic polarisation curves were cut into
coupons and encapsulated into epoxy resin so that only a surface
with the dimension of 10 mm  10 mm was exposed to the
500 ml of the solution. A platinum gauze (25 mm  25 mm, 52
mesh) was used as the counter electrode and a saturated calomel
electrode (SCE) was used as the reference electrode. All potentials
were referred to the SCE. The polarisation curves were used to ex-
plore the relationship, if any, between that electrochemical mea-
surements of the corrosion rate, based on the corrosion current
at the free corrosion potential, and direct measurements using
weight loss or evaluated from the evolved hydrogen. The corro-
sion current at the free corrosion potential was evaluated by Tafel
extrapolation of the cathodic branch of the polarisation curve. The
cathodic curves were all linear except for the curve measured in
the 0 M NaCl pH 7 solution; a slope was used similar to those of
the other plots.

3. Results

3.1. Microstructure

Fig. 1 presents optical and SEM micrographs of ZE41. The micro-

structure consisted of the primary a-Mg grains plus a second phase
(the b-phase) distributed along and/or adjacent to the boundaries
of the a -Mg grains; the b-phase distribution was non-continuous.
In addition, some b-phase particles appeared to be inside the a -Mg
grains as isolated particles. Details of EDS and XRD analyses of the
b-phase were described previously [8], these analyses were consis-
tent with Mg7Zn3(RE) and Mg12RE.
3.2. Hydrogen evolution
Fig. 2 presents the hydrogen evolution volume (ml/cm2), as a
function of immersion time, for ZE41 immersed in 0 M, 0.1 M
and 1 M NaCl solutions with pH 3, 7 and 11. The evolved hydrogen
volume was essentially zero for the 48 h immersion in 0 M NaCl
solutions with pH 7 and 11, which indicated that there was a
low corrosion rate for ZE41 in neutral or alkaline solutions without
chloride ions. For all other solutions, after an incubation period
during which there was a low hydrogen evolution rate, there was
an increase in hydrogen evolution volume with increasing immer-
sion time. The incubation period and rate of hydrogen evolution
depended on the solution. The incubation period decreased and
the hydrogen evolution rate increased with increasing chloride
ion concentration at each pH (Fig. 2a) and with decreasing pH for
each chloride ion concentration (Fig. 2b). For example, in the pH
3 solution with 0 M NaCl (Fig. 2a) the hydrogen evolution started
an obvious increase after 20 h and reached 2.9 ml/cm2 by an
immersion time of 48 h, whereas in the pH 3 solution with
1 M NaCl, the hydrogen evolution started an obvious increase after
1 h and reached 17.5 ml/cm2 by 48 h immersion. In the 1 M NaCl
pH 11 solution (Fig. 2b) the hydrogen evolution started an obvious
increase after 5 h and reached 7.0 ml/cm2 by 48 h, whereas in the
1 M NaCl pH 3 solution, an obvious increase started after 1 h and
reached 17.5 ml/cm2 by 48 h. The incubation time, and the hydro-
Fig. 1. ZE41 microstructure:(a) low magnification optical micrograph and (b)
higher magnification SEM micrograph.
gen evolution volume after 48 h immersion, are summarized in
Tables 2 and 3.
3.3. Corrosion rate
Fig. 3 presents the average hydrogen evolution rate (ml/cm2/
day) for ZE41 immersed in 0 M, 0.1 M and 1 M NaCl solutions of
pH 3, 7 and 11. The hydrogen evolution rate was essentially zero
for immersion in the 0 N NaCl solutions with pH 7 and 11. For
the other cases, the hydrogen evolution rate increased with
decreasing pH at each chloride ion concentration (Fig. 3a) and with
increasing chloride ion concentration at each pH (Fig. 3b). This
indicated that the corrosion rate of ZE41 depended on the com-
bined influence of pH and chloride ion concentration. The influence
of pH was the largest in the 1 M NaCl solution. The influence of
chloride ion concentration was largest at low chloride ion concen-
trations, for which the rate of increase was higher than at higher
chloride ion concentrations, although there was a much higher
hydrogen evolution rate at higher chloride ion concentrations for
each pH, Fig. 3b. The hydrogen evolution volume rate, VH
(ml cm2 d1) can be related to the corrosion rate, PH (mm y1)
using the following conversion equation [7,8,65,66]:
PH ¼ 2:279 V H ð2Þ
Table 4 presents the corrosion rate, evaluated from the average
hydrogen evolution rate, for immersion in the various solutions.
The highest corrosion rate was in the 1 M NaCl pH 3 solution.
 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178 3171

a 20
b 20
-
0 M Cl pH3
0.1 M Cl
- pH7
- pH11
15
1 M Cl 15

10 pH=3 10 0 M Cl
-

5 5

0 0
0 10 20 30 40 0 10 20 30 40

2
2

H2 evolution volume, ml/cm

H2 evolution volume, ml/cm

15 15

pH=7
10 10 -
0.1 M Cl

5
5

0
0
0 10 20 30 40
0 10 20 30 40

15 15

10 10

-
pH=11 1 M Cl
5 5

0 0
0 10 20 30 40 50 0 10 20 30 40 50
immersion time, h immersion time, h

Fig. 2. Hydrogen evolution volume as a function of immersion time.

Table 2 Table 3
Incubation time [h] for ZE41 immersed in the following chloride solutions Hydrogen evolution volume (ml/cm2) for ZE41 immersed for 48 h in the following
chloride solutions
pH 0 M NaCl 0.1 M NaCl 1 M NaCl
pH 0 M NaCl 0.1 M NaCl 1 M NaCl
3 20 5 1
7 >48 7 3 3 2.9 8.4 17.5
11 >48 7 5 7 0 2.1 11.9
11 0 1.4 7.0

3.4. Macroscopic corrosion morphology
Fig. 4 presents the macroscopic surface appearance of the cor-
roded samples at the end of the 48 h immersion period. There
was no obvious corrosion for the samples exposed to 0 M NaCl
pH 7 and 11 solutions indicating that the air formed film provided
resistance to corrosion initiation in the 0 M NaCl neutral or alkaline
solutions for at least 48 h. For all other samples, at the end of the
48 h immersion period, the whole surface was homogenously cov-
ered by a layer of corrosion products, indicating that the corrosion
was uniformly distributed over the whole surface (at least at the
macro-level). The amount of visible corrosion qualitatively
3172 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178

Table 4 pH 7 and 11 solutions; the incubation time was much longer than
Corrosion rate, pH (mm/y), evaluated from the average hydrogen evolution rate, for the experimental times of Fig. 5.
ZE41 immersed in various NaCl solutions
Group B contained the other curves. For group B, the open cir-
pH 0 M NaCl 0.1 M NaCl 1 M NaCl cuit potential curve had a maximum after several minutes, and
3 3.2 9.7 20 subsequently the potential decreased gradually to less noble val-
7 0 2.3 14 ues. The initial potential increase to a maximum was consistent
11 0 1.5 8.0 with an incubation period for the initiation of corrosion. However,
the incubation period evaluated from the open circuit potential
curve was much shorter than that evaluated from the hydrogen
gas evolution volume, Table 2 and Fig. 2, indicating that the elec-
a 9.0
trochemical technique was more sensitive in detecting the onset
-
0 M Cl
of corrosion than the technique based on hydrogen gas evolution.
H2 evolution volume rate, ml/cm day

-
7.5 0.1 M Cl
-
The subsequent decrease of the potential correlated with the
2

1 M Cl
6.0 occurrence of corrosion. The potential stabilised to a steady state
value reflecting the dynamic balance between the advance of the
4.5 corrosion and the deposit of the corrosion products; at steady state
all the sample surface was corroding. The steady state open circuit
3.0 potential decreased to less noble values with increasing chloride
ion concentration at each pH (Fig. 5a) and with decreasing pH at
1.5 each chloride ion concentration (Fig. 5b). In these cases, there
was a correlation between the open circuit potential and the corro-
0.0
0 2 4 6 8 10 12 14
sion rate as determined from the hydrogen evolution volumes gi-
ven in Tables 3 and 4, i.e. a more negative open circuit potential
pH value
correlated with higher hydrogen evolution volumes and higher
corrosion rates, consistent with the prior reports [67]. However,
b 9.0
the decrease in the open circuit potential was small for a decrease
pH3
H2 evolution volume rate, ml/cm day

7.5 pH7 in pH from 11 to pH 7 in the 0.1 M and 1 M solutions, which im-

2

pH11 plied that the chloride ion has a small influence.

6.0
4.5
3.0
1.5
0.0
0.0 0.2
Cl- concentration, M
Fig. 3. Hydrogen evolution rate as a function of (a) pH and (b) Cl concentration.
increased with chloride ion concentration at each pH and with
decreasing pH at each chloride ion concentration, in qualitative
agreement with the hydrogen evolution results as presented in
Fig. 3. As reported previously [8], and as observed in the present
study, the corrosion initiated as localised corrosion. The corrosion
initiated at some sites on the surface, subsequently expanded over
the whole surface and finally a layer of corrosion products covered
the whole surface.
3.5. Open circuit potential
Fig. 5 shows the evolution of the open circuit potential for ZE41
immersed in 0 M, 0.1 M and 1 M NaCl solutions with pH 3, 7 and
11. Each measurement series started immediately after immersion
of the ZE41 specimen in the test solution and reflected the initia-
tion and propagation of corrosion. The curves were in two clusters.
Group A contained the open circuit potential curves in 0 M NaCl pH
3, pH 7 and 11 solutions; the potential increased smoothly and
continuously. This correlated with the relatively long incubation
period for the initiation of corrosion in these solutions; visible cor-
rosion did not occur in the experimental period. The open circuit
potential data, Fig. 5 was consistent with the incubation time of
the hydrogen gas evolution volume data, Table 2; the incubation
period was long for the samples exposed to the 0 M NaCl pH 3,
3.6. Potentiodynamic polarisation curves
Fig. 6 presents the potentiodynamic polarisation curves for
freshly prepared ZE41 samples immediately after immersion in
0 M, 0.1 M and 1 M NaCl solutions with pH 3, 7 and 11. There
was a significant deviation from Tafel behaviour for the cathodic
curve in the pH 7, 0 M NaCl solution; this deviation was attributed
to measurement errors, particularly iR drop. All the other cathodic
0.4 0.6 0.8 1.0
curves showed Tafel behaviour, Fig. 6a. The extent of the cathodic
Tafel region related to the onset of pitting at just prior to the cor-
rosion potential, as was also noted by Song et al. [48–50]. There
was a rapid increase in the anodic curve in all the pH 11 solutions
and in the pH 7 solutions with 0.1 M and 1 M NaCl. In the pH 3
solutions there was also a rapid increase in the anodic curve and
there was an inflection point in each of these curves. This probably
indicates some sort of kinetic barrier effect, maybe the deposition
of a corrosion product film and then its removal by intensively
evolved hydrogen bubbles, which was more apparent at the higher
currents in the pH 3 solutions. ZE41 showed no classical passivity
type behaviour for any of the conditions studied.
The polarisation curves were used to estimate the corrosion
current density, icorr, at Ecorr, by Tafel extrapolation of the cathodic
branch. The corrosion current density, icorr (mA cm2), can be re-
lated to the corrosion rate, Pi (mm.y1), using the following conver-
sion equation [7,8,65,66].
Pi ¼ 22:85 icorr ð3Þ
Table 5 presents the corrosion rate, evaluated from the icorr data
for the freshly prepared ZE41 samples, for the various solutions.
The highest corrosion rate was for the 1 M NaCl pH 3 solution. A
comparison of the values in Table 4 with those in Table 5 indicated
that (i) the corrosion rates were much higher when estimated from
the hydrogen evolution rate and (ii) the corrosion rate estimated
from the Tafel extrapolation showed the same trends in influence
of pH and chloride ion concentration. The reason for the difference
may be that different types of corrosion were measured. The corro-
sion rate from the Tafel extrapolation may relate to the onset of
 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178
Fig. 4. Surface of the corroded samples after 48 h immersion.
corrosion, whereas the corrosion rate from the hydrogen evolution
measurements relates to corrosion averaged over a considerable
time period and includes corrosion some considerable time after
corrosion onset, when the corrosion is well established.
Fig. 7 presents the polarisation curves measured after 48 h
immersion in the solution and compares these curves with the
polarisation curves measured immediately after immersion in the
solution. There were large differences for each solution. For each
solution, the cathodic current (i.e. the rate of hydrogen evolution)
was significantly higher and the corrosion potential was signifi-
cantly more positive for the curves measured after 48 h immersion
in the solution compared with the curves measured with a fresh
sample. It was hoped that Tafel extrapolation would yield corro-
sion rates comparable to or related to those evaluated from the
hydrogen evolution rate, Table 4. Table 6 presents the corrosion
rate, Piss (estimated from icorr from polarisation curves measured
for ZE41 after reaching steady state corrosion conditions) com-
pared with the corrosion rate, Pio (estimated from icorr measured
from polarisation curves for freshly prepared ZE41) and the corro-
sion rate, PH (evaluated from the average hydrogen evolution rate)
for ZE41 immersed in various NaCl solutions. The corrosion rate,
Piss, was always greater than the corrosion rate, Pio, but the differ-
ence was small for the 0.1 M NaCl solutions whereas the difference
was larger in the 1 M NaCl solution. The trends for the corrosion
3173
rate, Piss (related to pH and chloride concentration) were similar
to those for the corrosion rate, PH; but any similarity of the numer-
ical value of Piss and PH appears fortuitous.
Fig. 8 presents the corrosion potential, Ecorr, determined from
the polarisation curves for freshly prepared ZE41 samples, Fig. 6,
as a function of chloride ion concentration (Fig. 8a) and pH
(Fig. 8b), for immersed in 0 M, 0.1 M and 1 M NaCl solutions with
pH 3, 7 and 11. Ecorr shifted to more negative (or more active) val-
ues with increasing chloride ion concentration at each pH (Fig. 8a)
and with decreasing pH at each chloride ion concentration
(Fig. 8b), showing similar tendencies as the open circuit potential.
Fig. 9 plots the measured value of steady state open circuit poten-
tial (from Fig. 5) or the corrosion potential (from Fig. 6) (both plot-
ted as Ecorr) against the corrosion rate as determined from (i) the
average hydrogen evolution volume rate from Table 4 and from
(ii) the Tafel extrapolated value of icorr, Table 5; a more negative
Ecorr value correlated with a higher corrosion rate.
4. Discussion
4.1. Hydrogen evolution
Many of the hydrogen evolution curves showed significant
increases in evolution rate over the 48 h immersion time. This
3174 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178

a 0N b
-1.2 0.1 N pH 3
1N -1.2
pH 7
pH 11
-1.3
-1.3

-1.4 -
-1.4 Cl = 0M
pH=3
-1.5
-1.5

-1.6
-1.6

-1.7
-1.7

0 200 400 600 800 1000 1200 1400 1600 180

-1.2 0 200 400 600 800 1000 1200 1400 1600
-1.2

Open circuit potentials, VSCE

Open circuit potentials, VSCE

-1.3
-1.3

-1.4 pH=7 -
-1.4 Cl = 0.1 M

-1.5
-1.5

-1.6
-1.6

-1.7
-1.7

0 200 400 600 800 1000 1200 1400 1600 1800

-1.2 -1.2 0 200 400 600 800 1000 1200 1400 1600

-1.3 -1.3

pH=11 -
-1.4 -1.4 Cl =1 M

-1.5 -1.5

-1.6 -1.6

-1.7 -1.7

0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000 1200 1400 1600 1800
Time, second Time, second

Fig. 5. Evolution of the open circuit potential.

indicates that steady state corrosion conditions take a significant
time to become established and that short-term measurements
can give rise to optimistically low values of corrosion rate.
4.2. Polarisation curves
There were significant differences between the polarisation
curves measured for freshly prepared samples and those measured
after the establishment of steady state corrosion conditions, Fig. 7.
This indicates that there are significant differences in the details of
the various electrochemical reactions under these two conditions.
For the freshly prepared samples, the cathodic reaction of hydro-
gen evolution occurs on the air formed film on the surface of the
freshly prepared surface. As shown by a number of studies [47–
50,68], the corrosion potential in chloride containing solutions re-
lates to the breakdown of the air formed film and the initiation of
pitting corrosion. For the sample that had attained steady state
corrosion conditions, the cathodic reaction, also assumed to be
hydrogen evolution, occurs on the corroded surface, possibly on
the surface of corrosion products, possibly Mg(OH)2. Clearly hydro-
gen evolution is much faster on the surface after steady state cor-
rosion has been attained.
In all cases, the steady state corroding surface had a free corro-
sion potential more positive than that of the freshly prepared sur-
face and moreover the steady state corroding surface had a higher
rate of hydrogen evolution. This means that, if a corroding area is
 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178 3175

a -0.6
b -0.6
0M
pH=3
0.1 M
pH=7
-0.8 1M
-0.8 pH=11

-1.0 -1.0

-1.2 pH=3
-1.2 -
0 M Cl

-1.4 -1.4

-1.6 -1.6

-1.8 -1.8
-7 -6 -5 -4 -3 -2 -7 -6 -5 -4 -3 -2

-0.8 -0.8

-1.0 -1.0
Potential, VSCE

-1.2 pH=7 Potential, VSCE -1.2

-
0.1 M Cl

-1.4 -1.4

-1.6 -1.6

-1.8 -1.8
-7 -6 -5 -4 -3 -2 -7 -6 -5 -4 -3 -2

-0.8 -0.8

-1.0 -1.0

-1.2 -
-1.2 1 M Cl
pH=11

-1.4 -1.4

-1.6 -1.6

-1.8 -1.8
-7 -6 -5 -4 -3 -2 -7 -6 -5 -4 -3 -2
- 2 - 2
log (current density) or log (I), A cm log (current density) or log (I), A cm

Fig. 6. Potentiodynamic polarisation curves measured immediately after immersion in the solution.

Table 5 the surface. This is indeed what is observed experimentally. The

Corrosion rate, Pio (mm/y), estimated from the icorr, measured for freshly prepared
ZE41 exposed to various NaCl solutions
galvanic acceleration of the corrosion of the non-corroding areas
(i.e. the spread of corrosion across the non-corroding areas), is bal-
pH 0 M NaCl 0.1 M NaCl 1 M NaCl anced by the galvanic protection of the corroded areas, so that the
3 0.93 3.7 5.0 corrosion tends to be rather shallow in the corroded areas. This is
7 0.16 0.63 1.6 also consistent with the observations. This spread of corrosion
11 0.09 0.22 0.60
across the surface for ZE41 in the present study was similar to
the observation for MEZ by Song [47] and in contrast to the ten-
dency for pitting for AZ91 observed by Song [47]. The critical as-
adjacent to a non-corroded area, there will be a galvanic cell caus- pect is that the corrosion potential of the corroded areas is more
ing the galvanic acceleration of the corrosion rate of the non-cor- positive than that of the fresh surface for ZE41 and MEZ, whereas
roded area. Thus, once corrosion starts, there is an for AZ91 the corrosion potential of the corroded areas is more neg-
electrochemical driving force for the spread of the corrosion across ative than that of the fresh surface.
3176 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178

a -1.0 a -1.1
0.1 M pH3 with 48 h pH 3
-1.1 0.1 M pH3 with 0 min -1.2 pH 7
0.1 M pH11 with 48 h pH 11
0.1 M pH11 with 0 min
-1.2
-1.3
Potential, VSCE

Ecorr, VSCE
-1.3
-1.4
-1.4
-1.5
-1.5

-1.6 -1.6

-1.7 -1.7
0.0 0.2 0.4 0.6 0.8 1.0
-1.8
-
Cl concentration, M
-7 -6 -5 -4 -3 -2
-1.1
log (current density) or log (I), A cm
- 2
b
0M
0.1 M
-1.2
b 1 M pH3 with 48 h
1M

1 M pH3 with 0 min

-1.3 -1.3
1 M pH7 with 48 h
1 M pH7 with 0 min

Ecorr, VSCE
-1.4
-1.4
Potential, VSCE

-1.5
-1.5
-1.6

-1.6
-1.7
0 2 4 6 8 10 12 14
-1.7 pH value

Fig. 8. Corrosion potential as a function of (a) Cl concentration and (b) pH.
-1.8
-7 -6 -5 -4 -3 -2
- 2
log (current density) or log (I), A cm -1.1
data from hydrogen evolution rate
Fig. 7. Polarisation curves measured after 48 h immersion in the solution compared data from icorr
-1.2
with curves measured immediately after immersion in the solution.

-1.3
Ecorr, VSCE

Table 6
The corrosion rate, Piss (estimated from icorr from polarisation curves measured for -1.4
ZE41 after reaching steady state corrosion conditions) compared with the corrosion
rate, Pio (estimated from icorr measured from polarisation curves for freshly prepared -1.5
ZE41) and the corrosion rate, PH (evaluated from the average hydrogen evolution rate)
for ZE41 immersed in various NaCl solutions
-1.6
pH 0.1 M NaCl 1 M NaCl
PH Pio Piss PH Pio Piss -1.7
0 5 10 15 20
3 9.7 3.7 4.5 20 5.0 17.0
7 2.3 0.63 – 14 1.6 3.2 Corrosion rate, mm/y
11 1.5 0.22 0.3 8.0 0.6 –
Fig. 9. Corrosion potential plotted against the corrosion rate.
The units for the corrosion rate were mm/y.

potential, did not agree with direct measurements evaluated from

4.3. Electrochemical measurement of corrosion rate
The electrochemical measurements were included to explore
the relationship, if any, between that electrochemical measure-
ments of the corrosion rate, based on the corrosion current at the
free corrosion potential, and direct measurements using weight
loss or evaluated from the evolved hydrogen, because of the known
[2,10,46,47] issue that electrochemical measurements of the corro-
sion rate, based on the corrosion current at the free corrosion po-
tential, do not agree with direct measurements using weight loss
or evaluated from the evolved hydrogen. Table 6 showed that the
corrosion rate determined from the current at the free corrosion
the evolved hydrogen.
Of most concern may be that there did not appear to be any
relation between Piss and PH. PH is the corrosion rate evaluated
from the average hydrogen evolution rate. There is substantial evi-
dence [2,7,48] that PH is a valid measure of the corrosion rate for
Mg alloys, equivalent to that of weight loss rate. Piss is the electro-
chemical measurement of corrosion rate (by Tafel extrapolation)
after steady state corrosion conditions had been attained. How-
ever, any similarity of the numerical value of Piss and PH appears
fortuitous; the ratio PH/ Piss varied seemingly randomly between
5.0 and 1.2 (the values are given in Table 7). The ratio PH/ Piss would
be expected to be a constant if the only factor was the negative
 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178
Table 7
Ratios PH/Pio and PH/Piss based on the data in Table 7
pH 0.1 M NaCl 1 M NaCl
PH/Pio PH/Piss PH/Pio
3 2.6 2.2 4.0
7 3.7 – 8.8
11 6.8 5.0 13.3
difference effect and if k was a constant, where k is the fraction of
the uni-positive Mg ion, Mg+, that undergoes chemical reaction
with water to liberate hydrogen. However, it is worth remember-
ing the work of Petty et al. [69] indicated that k need not be a con-
stant. In fact, due to the ‘‘anodic hydrogen evolution” phenomenon,
the corrosion rate of a magnesium alloy estimated from its polari-
sation curve is in theory not reliable [47]. The comparison of corro-
sion rates obtained by hydrogen evolution and polarisation curve
measurements in this study further confirmed the ‘‘anodic hydro-
gen evolution” effect [47].
4.4. Ecorr versus Corrosion rate
In this study more negative values of Ecorr correlated with a
higher corrosion rate, Fig. 9. Is this a general phenomenon for Mg
alloys? Maybe not. A plot of Ecorr versus corrosion rate from the
work of Song et al. [44] generated a seemingly-random scatter plot.
Südholz et al. [33] did carry out extensive measurements of Ecorr
and icorr but did not publish any measurements relating directly
to corrosion rate. These results are hard to use in their present ver-
sion because of the fact that there may be no relationship between
icorr and the corrosion rate for Mg alloys.
4.5. Corrosion mechanism
The corrosion behaviour and electrochemical behaviour of ZE41
is significantly influenced by pH and chloride ion concentration.
This corrosion behaviour is consistent with the current under-
standing that the corrosion behaviour of magnesium alloys is gov-
erned by the characteristics of its surface film [1–3,48–50]. The
surface film on magnesium alloys in aqueous solutions is thought
to be mainly Mg(OH)2 [1,2,6]. The corrosion reactions are pre-
sented by the following equations.
Mg ) Mg2þ þ 2e
2H2 O þ 2e ) H2 þ 2ðOHÞ
Mg2þ þ 2ðOHÞ ) MgðOHÞ2
Eq. (6) describes the surface film formation, this occurs because
Mg2+ has a low solubility. The influence of pH on corrosion needs to
take into account the magnesium E-pH diagram (Pourbaix dia-
gram) [70]. Thermodynamics and the E-pH diagram predict that
there should no film on a magnesium surface in a solution with a
pH lower than 10.5 because Mg(OH)2 is not stable under such con-
ditions (the pH value required for the precipitation of Mg(OH)2 is
around 10.5). However, even though the surface film is not ther-
modynamically stable at low pH values, the dissolution kinetics
may be slow and a surface film may be formed provided the disso-
lution kinetics are slower than the formation kinetics. Further-
more, a pH value over 10 was theoretically calculated and
experimentally measured in the electrolyte layer near a corroding
magnesium electrode, even though the bulk solution had a pH va-
lue as low as 4 [71], i.e. there is significant alkalization near the
magnesium surface in an acidic medium and this alkalization is
associated with the formation of surface film. This alkalization is
consistent with Eq. (5).
3177
The corrosion rate of ZE41 increased with decreasing pH and
increasing chloride ion concentration. This corrosion behaviour is
consistent with the current understanding that the corrosion
PH/Piss behaviour of magnesium alloys is governed by a partially protec-
tive surface film [1–3,48–50], with the corrosion reactions occur-
1.2
2.8
ring predominantly at the breaks or imperfections of the partially
– protective film. The implication is that the fraction of film free sur-
face increases with decreasing bulk pH and with increasing chlo-
ride ion concentration. This is consistent with the known
tendency of chloride ions to cause film breakdown, and the known
instability of Mg(OH)2 in solutions with pH less than 10.5.
5. Conclusions
1. The corrosion of ZE41 in NaCl chloride solutions depended on
the pH and the chloride ion concentration. A shorter incubation
period to the onset of corrosion; a more negative open circuit
potential and corrosion potential; and a higher corrosion rate
correlated with a higher chloride ion concentration at each pH
and correlated with a lower pH for each chloride ion
concentration.
2. The most active corrosion potential and the highest corrosion
rate occurred for ZE41 in the 1 M NaCl pH 3 solution. The corro-
sion rate was small in the 0 M NaCl pH 7 and 11 solutions.
3. The influence of chloride ion concentration was largest at low
chloride concentrations, for which there was a higher rate of
increase than at higher chloride concentrations.
4. This corrosion behaviour is consistent with the current under-
standing that the corrosion behaviour of magnesium alloys is
governed by a partially protective surface film, with the corro-
sion reactions occurring predominantly at the breaks or imper-
fections of the partially protective film. The implication is that
the fraction of film free surface increases with decreasing bulk
pH and with increasing chloride ion concentration. This is con-
sistent with the known tendency of chloride ions to cause film
breakdown, and the known instability of Mg(OH)2 in solutions
with pH less than 10.5.
5. The steady state corroding surface had a free corrosion potential
more positive than that of the freshly prepared surface and
moreover the steady state corroding surface had a higher rate
ð4Þ of hydrogen evolution. Galvanic interaction between the cor-
roding and non-corroding surface provides a driving force for
ð5Þ the spread of the corrosion over the whole surface and more-
over tends to decrease the corrosion rate of the corroding area
causing the corrosion penetration to be relatively shallow.
ð6Þ
6. The trends for the corrosion rates, Piss and Pio (related to pH and
chloride concentration) were similar to those for the corrosion
rate, PH; but any similarity of the numerical value of Piss and
PH appears fortuitous. Piss was estimated from icorr from polari-
sation curves measured for ZE41 after reaching steady state cor-
rosion conditions, Pio was estimated from icorr measured from
polarisation curves for freshly prepared ZE41 and PH was eval-
uated from the average hydrogen evolution rate.
7. The electrochemical measurements of the corrosion rate, based
on the corrosion current at the free corrosion potential, did not
agree with direct measurements evaluated from the evolved
hydrogen, in agreement with other observations for Mg.
Acknowledgements
This work was supported by the ARC Center of Excellence, De-
sign of Light Alloys. Ming-Chun Zhao, Ming Liu and Andrej Atrens
would like to thank EMPA for their support that allowed them to
3178 M.-C. Zhao et al. / Corrosion Science 50 (2008) 3168–3178

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