Electrochimica Acta 56 (2011) 7880–7884

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Investigations of pitting corrosion of magnesium by means of DEIS and

acoustic emission
Juliusz Orlikowski ∗ , Kazimierz Darowicki
Department of Electrochemistry, Corrosion and Materials Engineering, Gdańsk University of Technology, Narutowicza Str. 11/12, 80-952 Gdańsk, Poland

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

Article history: The paper presents methodology and results of electrochemical examination of magnesium in 0.1 M NaCl
Received 2 July 2010 solution with different pH. The measurements were conducted under potentiodynamic conditions using
Received in revised form 6 December 2010 Dynamic Electrochemical Impedance Spectroscopy (DEIS). Analysis of DEIS results was performed based
Accepted 6 December 2010
on electrical equivalent circuit. As the result of analysis changes of separate parameters of the equivalent
Available online 15 December 2010
circuit vs. potential for different pH values of the environment were obtained. Simultaneously with DEIS
measurements an investigation using acoustic emission was conducted. The results showed that for pH
Keywords:
higher than 12.50 the properties of layers on the surface of magnesium change significantly. One can
Magnesium
Pitting corrosion
observe a stable passive state that has properties considerably different from those of the layers that
DEIS form in solutions with lower alkalinity. In such conditions the beginning of pitting corrosion process
can be unequivocally determined by the level of acoustic emission and the values of electrochemical
parameters.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction possibility of passive state forming on the surface of magnesium in

The mechanism of corrosion of magnesium and its alloys has
been the subject of many investigations that have lately been even
more intensified. In environments that contain chloride ions corro-
sion of magnesium is mostly the result of negative difference effect
(NDE), which has not yet been fully investigated. It is also consid-
ered that the presence of oxide or hydroxide layer is a significant
factor in corrosion process, since those layers cannot constitute a
solid barrier protection in neutral or slightly basic environments
[1,2]. Currently, the most widely used electrochemical method that
enables precise evaluation of the state of layers on the surface
of magnesium and its alloys, as well as the investigation of cor-
rosion mechanism, is impedance measurement [2–5]. However,
this method cannot be used for examining non-stationary pro-
cesses, e.g. active–passive states. For investigating basic properties
of surface layers one uses microscopic and ellipsometric methods
[3,6–10]. The presence of films on the surface of magnesium and
its alloys contributes to corrosion that has local character [2,9].
Detailed research showed that the result of corrosion of magne-
sium and its alloys are characteristic pits [6,11]. It was also found
that evaluation of corrosion processes and thus the forms of cor-
rosive attack depend as well on the constitution of the alloy and
its microstructure [4,6,8]. The research of Hara et al. indicates the
∗ Corresponding author. Tel.: +48 583472283; fax: +48 583471092.
E-mail addresses: zak@chem.pg.gda.pl, juliuszo@chem.pg.gda.pl,
juliuszo@plusnet.pl (J. Orlikowski).
0.1 M NaCl (for pH = 6.1) [7]. During longer exposition in this envi-
ronment one observes an effect that can be considered the result
of the presence of passive state. This effect manifests itself during
further polarization measurements as a weak dependence of cur-
rent on potential [7]. However, considering a relatively low value
of the environment’s pH and relating it do Pourbaix diagram one
can suppose that the formed film does not have full barrier prop-
erties, which are characteristic for passive layers [7]. The layer that
forms on the surface of magnesium in environments with higher
pH should have those properties. Potentiodynamic measurements
conducted by Liu et al. in 0.1 M NaCl solution with pH = 12 showed
that in passive state current is much lower, which indicates that
the properties of passive layers are different than those observed
during measurements in environments with lower pH, particu-
larly that high anodic polarization in strongly basic environments
contributes to improvement of passive layer’s barrier properties
[3,5,12].
Based on the literature overview it can be stated that corrosion
of magnesium and its alloys in chloride ions environment leads
to pitting corrosion when stable passive layer or porous untight
layer is present on the metal’s surface. When considering the initi-
ation of corrosion process, barrier properties of films formed on the
metal’s surface become important. Therefore, it is crucial to estab-
lish how the initiation of corrosion proceeds under conditions of
complete and incomplete passivity. The aim of the work presented
in this paper is the impedance analysis of magnesium corrosion in
basic environment and in the presence of chloride ions. A signif-
icant part of this work includes specifying the properties of the

0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.12.021
 J. Orlikowski, K. Darowicki / Electrochimica Acta 56 (2011) 7880–7884
layers on magnesium’s surface and their influence on corrosion
process. To obtain this goal, DEIS method was used. The method
was already successfully applied to investigating pitting corrosion
of steel and aluminium alloys [13–15]. This relatively new mea-
surement method is highly suitable for investigating active–passive
states that appear in basic environment in the case of magnesium
and its alloys.
2. Experimental
Subjected to experiments were specimens of magnesium of
3N purity and 1 cm2 surface. Electrochemical measurements were
conducted in 0.1 M NaCl environment for different pH that was
changed by adding NaOH. The measurements were held for
pH = 8.50, 9.50, 10.50, 11.50, 12.00, 12.50, 12.66, 12.75, 13.00.
In order to improve the clarity of presented results only cho-
sen measurements results were plotted in figures. Electrochemical
investigation was conducted in a three-electrode system with
calomel electrode (SCE). The electrochemical measurements were
performed by means of the Dynamic Electrochemical Impedance
Spectroscopy technique. This method is general and allows the
analysis of impedance spectra in joint time–frequency domain. The
analysing window is applied to cut a fragment out of the recorded
register. In the next step this fragment is subjected to Regular
Fourier Transformation and instantaneous spectrum is obtained.
The main advantages of this method compared to the classical
impedance technique are as follow:
• one can receive instantaneous impedance spectra instead of aver-
age ones (“frequency by frequency” technique), which reflect the
dynamics of investigated process;
• allows the examinations of non-stationary electrochemical pro-
cesses in time domain.
The DEIS measurements were realized using KGLstat v. 2.1
potentiostat and a National Instruments PCI 6120 card that gen-
erated the perturbation signal, as well as registered voltage
perturbation and current response signals. Impedance measure-
ments were executed for the frequency range: 20 kHz–0.3 Hz. The
average number of points per decade in the DEIS measurements
was 5. Sampling frequency of 100 kHz resulted from the mea-
surement card settings being at our disposal. Multi-sinusoidal
signal composed of 20 sinusoids was used for the experiments.
The applied frequencies were meant to be in a good agreement
with the ranges of interest for the system under examination.
Depending on applied frequency, the amplitudes sinusoids ranged
from 3 to 18 mV. Frequency selection was aimed at elimination
of overlapping of eventual harmonic components of particular
frequencies. Detailed description of this measurement method
can be found in the literature [16,17]. Acoustic emission mea-
surements were executed by means of the two-channel system,
Mistras 2001. Analysis of obtained data was performed using
Mistras standard software. Acoustic emission and DEIS measure-
ments were conducted simultaneously under potentiodynamic
conditions. The measurements were carried out from stationary
potential towards negative potentials. Rate of potential changes
was 1 mV/s.
3. Results and discussion
Fig. 1 presents exemplary impedance spectrograms measured
using DEIS method under potentiodynamic conditions for different
pH of 0.1 M NaCl solution.
In Fig. 1a and b the impedance decreases with the increase of
potential that is the result of proceeding corrosion of magnesium.
7881
For high anodic potentials the impedance does not change sig-
nificantly. The character of impedance changes plotted in Fig. 1c
and d is similar to those from Fig. 1a and b, however, impedance
values are higher in plots c and d, which indicates lower kinetics
of corrosion processes. The character of impedance changes plot-
ted in Fig. 1e differs significantly from the other three. In this plot
the impedance does not change for potentials from −1.3 V to −1 V.
Also, the impedance values are high in this potential range, which
can prove the existence of stable passive state. For polarization
higher than −1 V impedance suddenly decreases, which indicates
the beginning of corrosion process. Impedance spectra presented
in Fig. 1f do not exhibit any changes with potential and repre-
sent stable passive state. In order to match an electrical equivalent
circuit, two assumptions have been made. They are schematically
presented in Fig. 2.
During polarization measurements of magnesium electrochem-
ical and physicochemical processes proceed in two ways. When
the passive layer is stable and tight (Fig. 2a) the overall impedance
of the system is related to resistance (Rf ) and capacitance (Cf ) of
the passive layer. If, however, the layer is untight (Fig. 2b), then
we can expect the corrosion of magnesium to proceed in the spots
where layer’s defects occur. This process is described by the resis-
tance of charge transfer (Rp ) and the capacitance of duble layer (Cdl ).
For intermediate cases the current will be conducted in both ways
simultaneously. Considering the limited range of frequencies that
can be used in DEIS measurements, the equivalent circuit was fur-
ther simplified. The final equivalent circuit used for the analysis of
impedance spectra is presented in Fig. 3.
In Fig. 3 R1 represents the resistance of electrolyte, R2 represents
the resistance of passive layer or charge transfer resistance and CPE
element (Q) represents the capacitance of double electrical layer
or, in the passive state, the capacitance of passive layer. In Fig. 4
exemplary plots of R2 vs. potential are presented.
Dependencies involved with R2 changes depiected in Fig. 4 are
presented as a function of potential including ohmic drop. The size
of this correction was determined based on the analysis of elec-
trolyte’s resistance (R1 ) and DC current obtained by filtering DEIS
measurements conducted for different pH values. In Fig. 4 the scale
of R2 values is logarithmic. This simplifies the comparison between
the plots obtained for different pH values.
If we analyse the changes of R2 vs. potential we will see that for
pH = 12.75 the character of these changes differs significantly from
the plots obtained for lower pH. The values of resistance in this
case are more than 10 times higher than for other measurements.
Moreover, in the initial range of potentials R2 varies only a little
(these variations are not bigger than 10% of the measured resistance
value) whereas for other pH values R2 decreases from the begin-
ning to the end of the measurement. Furthermore, for pH = 12.75
we can observe a drop of R2 that is much more steep than in the
other three cases. The character R2 changes for pH = 12.75 can be
explained by a sudden loss of tightness of the passive layer. In this
case R2 initially represents the resistance of passive layer. After the
layer cracks, the corrosion proceeds and R2 represents the charge
transfer resistance, related to the propagation of pitting corrosion.
More smooth changes of R2 for lower pH values suggest that in
those cases there is no stable passive state from the beginning of
the measurements. The character of R2 changes indicates that cor-
rosion processes evolve with the increase of polarization. There is
no initiation and fast propagation of pitting corrosion in this case.
Local, as well as general corrosion proceed. In the case of measure-
ments realized in the electrolyte solution of pH = 13.00 values of R2
resistance do not change as a function of potential indicating stable
passive state.
They are related to the incomplete passivation of magnesium’s
surface. Fig. 5 presents the changes of Q (CPE) vs. potential for
different pH values.
7882 J. Orlikowski, K. Darowicki / Electrochimica Acta 56 (2011) 7880–7884

Fig. 1. Impedance spectrograms vs. potential obtained for selected DEIS measurements in environments with pH = 8.50 (a), pH = 10.50 (b), pH = 12.50 (c), pH = 12.66 (d),
pH = 12.75 (e), and pH = 13.00 (f).

The plots presented in Fig. 5 show that with the increase of
polarization level the value of Q also increases for all pH values.
However, the dynamics of these changes are lower for higher pH.
For pH = 12.75 and 13.00 the change of Q parameter is almost unno-
ticeable. In order to confirm the presence of full passive state for
pH = 12.75 further measurements with the use of acoustic emis-
sion were conducted. Figs. 6 and 7 present the number of acoustic
emission events vs. potential for pH = 12.50 and 12.75, respectively.
Acoustic emission is a very useful technique for the mea-
surements of active–passive states, related to the initiation and
 J. Orlikowski, K. Darowicki / Electrochimica Acta 56 (2011) 7880–7884
Fig. 2. Assumption made for the electrical equivalent circuit used for analysis of impedance spectra obtained with DEIS measurements.
Fig. 3. Electrical equivalent circuit used for the analysis of DEIS measurements.
propagation of pitting corrosion. It has proved particularly useful
for investigating pitting corrosion of stainless steel [15]. In the case
of pitting corrosion initiation acoustic signals’ emission is caused by
the cracking of passive layer, whereas during propagation stage the
analyzed acoustic effects are related to hydrogen emission. In Fig. 6
we can observe that for pH = 12.50 the number of acoustic events
gradually increases with potential. For pH = 12.75 (Fig. 7) the num-
ber of acoustic events is initially low and does not change with the
increase of anodic polarization. A sudden increase of the number of
events appears when the potential exceeds 1.05 V. For deeper polar-
ization the number of events stabilizes. Measurements conducted
for pH lower than 12.50 showed that the character of changes of the
number of acoustic events is similar to the one presented in Fig. 6,
which indicates that the properties of the layers on magnesium’s
surface are similar for pH ranging from 9.50 to 12.50. Significant
differences in acoustic emission results presented in Fig. 7 indicate
the presence of a stable passive layer on magnesium’s surface for
Fig. 4. Changes of R2 vs. potential obtained by analyzing DEIS measurements using
the equivalent circuit (Fig. 3) for pH =  9.50, 10.50, × 12.50,  12.66, – – – 12.75,
and — 13.00.
7883
Fig. 5. Changes of Q vs. potential obtained by analyzing DEIS measurements using
the equivalent circuit (Fig. 3) for pH =  9.50, 10.50, × 12.50,  12.66, – – – 12.75,
and — 13.00.
pH = 12.75. In passive state acoustic activity is very low, which can
be observed in Fig. 7 for potentials ranging from −1.39 V to −1.05 V.
The sudden increase in the number if acoustic events for −1.5 V is
the result of the passive layer’s cracking. Further acoustic activity is
related to the proceeding of pitting corrosion. For pH ranging from
9.50 to 12.50 we do not observe the presence of full passive state
and, therefore, acoustic activity increases steadily with potential.
Fig. 8 presents a microscopic image of the surface of magnesium
specimen after performing measurements for pH = 12.50.
The image in Fig. 8 shows a large number of local damages. Size
and depth of the observed corrosion attacks are relatively small.
Fig. 6. The number of acoustic events vs. potential for pH = 12.50.
7884 J. Orlikowski, K. Darowicki / Electrochimica Acta 56 (2011) 7880–7884
Fig. 7. The number of acoustic events vs. potential for pH = 12.75.
Fig. 8. Microscopic image of the surface of magnesium specimen after performing
DEIS measurements for pH = 12.5, 100× magnification.
Fig. 9. Current changes vs. potential obtained for DC current polarization measure-
ments for for pH =  9.50, 10.50, × 12.50,  12.66, – – – 12.75, and — 13.00.
When corrosion proceeds under conditions of incomplete passiva-
tion of magnesium’s surface, corrosion attacks occur in many spots.
The process proceeds non-uniformly because of diversified prop-
erties of the untight oxide layer. Fig. 9 fully confirms the obtained
results. It presents the results of DC current polarization measure-
ments obtained by filtering DEIS measurements.
In the plots obtained for pH from 9.50 to 12.50 it is difficult to
distinguish the passive range, because the current increases fast
with the increase of potential. For pH = 12.75 we can clearly see
the passive range, as well as the point of initiation of pitting cor-
rosion, which results in sudden increase of DC current. In the case
of measurements performed in the solution of pH = 13.00 one can-
not observe changes of DC current with potential indicating stable
passive state.
4. Conclusions
Several conclusions can be drawn based on the analysis of con-
ducted measurements:
• Corrosion process detected in environments with pH ranging
from 9.50 to 12.50 can be characterized by local attacks occur-
ring under conditions of partial passivation of magnesium surface
only. It is difficult to observe the passive range in polarization
plots. Charge transfer resistance decreases with the increase of
anodic polarization, whereas the level of acoustic events gradu-
ally increases.
• For pH = 12.75 the proceeding pitting corrosion is related to the
complete passivation of metal’s surface. The passive range is
clearly noticeable in the polarization plot. Value of R2 obtained
by analyzing DEIS measurements drops suddenly for E = −1.05 V,
which corresponds to the sudden increase of acoustic activity.
The observed corrosion pits are deep and considerably large.
• It should be noticed that analyzing the forms of corrosive attacks
based only on the microscopic images of the surface may lead
to incomplete conclusions. It is not a solid rule that attacks in
the form of local corrosion defects are caused by pitting corro-
sion related to stable passive state. The observed attacks may as
well be the result of general corrosion or corrosion related to par-
tial passivation of the surface. This may lead to false conclusions
regarding the mechanism and kinetics of corrosion processes.
• The methodology used in presented work enables accurate dis-
tinction between the barrier properties of the layers based on
electrochemical measurements. This can considerably simplify
further investigations of corrosion mechanism.
Acknowledgment
This work has been supported by grant no. N N507 452734
financed by Polish Ministry of Education and Science.
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