Progress in Organic Coatings 89 (2015) 1–7

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Investigation by electrochemical impedance spectroscopy of filiform

corrosion of electrocoated steel substrates
A.-P. Romano ∗ , M.-G. Olivier
University of Mons – UMONS, Faculty of Engineering Materials Science Department, Place du Parc 20, 7000 Mons, Belgium

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

Article history: This work aims at studying by electrochemical impedance spectroscopy (EIS) the susceptibility to filiform
Received 19 February 2015 corrosion of low carbon steel covered by cataphoretic coating. The determination of the exposed metallic
Received in revised form 7 May 2015 area variations of scratched samples during ageing test is an estimation of the disbonding of the coating
Accepted 21 May 2015
and/or the filiform corrosion. This area can be evaluated by electrochemical impedance spectroscopy
(EIS). A simplified electrical equivalent model used to estimate the exposed metallic area is valid if the
Keywords:
corrosion products are correctly dissolved before characterization. Furthermore the steel is a very com-
Filiform corrosion
plex substrate and thus many parameters must be optimized in order to remove the corrosion products
Steel
Delamination
before EIS measurements.
EIS
© 2015 Elsevier B.V. All rights reserved.

1. Introduction of the coating to water and oxygen [11,12], adherence of the paint
system and the presence of salts [13].
In automotive industry, the body car is composed of different In addition electrochemical impedance spectroscopy (EIS) is a
metallic substrates such as steel, hot dip galvanized steel and alu- useful tool to evaluate the efficiency of new coatings such as barrier
minium alloys of 6016 series. The hot dip galvanized steel is for properties and water uptake of organic coating [14], cut edge corro-
the majority of cars the most used substrate due to its sacrificial sion [15,16], delamination process and filiform phenomena [17]. As
properties. For economic reasons such as treatment cost of galva- shown in previous papers, EIS can be used to evaluate the sensitiv-
nization process and availability and cost of zinc, steel substrate ity to filiform corrosion through the estimation of exposed metallic
has been recently more and more investigated and reused without area. More particularly filiform corrosion of aluminium was pre-
sacrificial protection in car industry. The corrosion protection of all viously evaluated by EIS on scratched coated samples [18,13,19].
the metallic parts of the body car is often obtained by a first organic The method used is based on the electrical equivalent model pro-
layer applied by cataphoresis. Furthermore steel substrate is very posed by Kendig [20,21]. This circuit consists of two time constants
reactive and sensitive to corrosion and also to filiform corrosion (Fig. 1). The first time constant observed at high frequency is related
when organic coated. This specific type of corrosion is produced to the coating properties.
between the coating and the substrate by formation of filaments In the case of a very low coating capacitance (10−10 F/cm2 ) and
[1]. In the presence of defect in the organic coating, galvanic corro- a large defect as a scratch, this time constant is generally shifted
sion develops between the head front of the filament (anode) and towards higher frequencies than those reached with usual proce-
the tail (cathode) [2–4]. At the anode, the most important reac- dures.
tion is the oxidation of the iron while at the cathode, the tail of the The second time constant, at low frequency, takes into account
filament is the area where the reduction of O2 in OH− ions occurs. the corrosion reaction of the metallic substrate. This time constant
This corrosion phenomenon can induce delamination of the coating is characterized by the double layer capacitance Cdl and an element
and formation of corrosion products (iron oxides and hydroxides). Zf which contains the charge transfer resistance Rct and electrical
Numerous parameters influence filiform corrosion such as metallic elements taking into account the low frequency behaviour which
substrate [5–8] but only few data are reported for the steel substrate appears when iron dissolution takes place [22]. Cdl and Rct are two
[7,8], surface preparation [9,10], presence of defects, permeability parameters which can be used to specify the sensitivity of the sys-
tem to delamination or filiform corrosion. The active metallic area
is proportional to the electrical parameters related to this time con-
∗ Corresponding author. stant. Such an equivalent circuit is valid for the study of scratched
E-mail address: [email protected] (A.-P. Romano). organic coatings considering that the resistance under the film is

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2 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7

Industries, France. The applied voltage was determined in order to

obtain a film thickness of 20 ␮m ± 1 ␮m. The bath temperature was
30 ◦ C. The samples were coated for 3 min, rinsed and cured in an
oven at 175 ◦ C for 25 min.

2.2. EIS

2.2.1. Electrochemical measurements

A conventional three-electrode cell was used for the electro-
chemical tests. The working electrode was the investigated sample
(exposed area of 4.5 cm2 ), the counter electrode was a platinum
plate and all potentials were measured with respect to an Ag/AgCl
(+0.205 V vs SHE) reference electrode. The cell was placed in a Fara-
Fig. 1. Electrical equivalent circuit used to study filiform corrosion. Rs is the bulk day cage in order to minimize external interference on the system.
electrolyte resistance, Cc the coating capacitance, Rp the pore resistance of the coat-
The impedance measurements were carried out over frequencies
ing, Cdl the double layer capacitance and Zf an element representing the faradic
impedance. ranging from 100 kHz to 10 mHz, at ambient temperature. The
impedance spectra were acquired by using a potentiostat coupled
with a frequency response analyser (Parstat 2273 from Ametek),
sufficiently low. EIS in that case can get quantitative information computer-controlled with Powersuite® software.
about filiform corrosion or delaminated area. This technique can be Electrochemical impedance measurements were performed on
used to evaluate in short time the sensitivity to filiform corrosion bare and scratched coated samples following the procedure devel-
compared to the classical evaluation of this type of corrosion. The oped on the aluminium alloys [17]. The coated samples used for this
estimation of the exposed area is possible if the corrosion products test were scratched with a cutter reaching the metallic substrates.
are correctly dissolved before characterization. Their presence may The linear defect produced was 2 ± 0.02 cm long and 40 ␮m width
indeed hinder the metal activity leading to an underestimation of with an area about 0.8 mm2 (measured accurately).
the delaminated area. In order to remove the corrosion products The procedure used to initiate and propagate filiform corrosion
and to avoid subsequent corrosion during the measurement, many was the same adopted in the ISO/DIS 4623-1 standard. Filiform cor-
parameters must be optimized. The procedure used for aluminium rosion was inoculated by exposure to HCl vapours for 1 h and the
substrates [17] needs to be adapted for steel substrate taking into samples were then placed in a humidity chamber at 82 ± 3% relative
account that steel corrosion in acid medium is active, corrosion humidity and 40 ± 2 ◦ C. The exposure time to the climatic chamber
products characterized by a high specific volume can be dissolved was limited to 24 h. After dissolution of the corrosion products, the
in acidic medium and steel is passive in alkaline medium [23]. The samples were analyzed by EIS at room temperature with a signal
initial proposed approach discussed in this paper is based on a two- amplitude voltage of 5 mV rms. Each measurement was repeated
step approach: first step which consists of a fast corrosion product three times, each time using a different sample.
dissolution in acidic medium and the second step which is the EIS
evaluation in alkaline medium electrolyte in which steel is passive.
2.2.2. Equivalent circuit interpretation
The parameters to optimize are the choice of acid, the dissolution
The equivalent circuit model used to interpret the EIS data of
time, the EIS electrolyte, immersion time before EIS measurements
coatings with an artificial defect in an alkaline solution is given in
and finally the exposure time to humidity chamber before estimat-
Fig. 2. In this solution, steel is known to be passive. This circuit con-
ing the exposed metallic area.
sists in the uncompensated electrolyte solution resistance between
the reference and the working electrode Rs , the non-ideal capaci-
2. Experimental tance (all the capacitances are mathematically modelled using a
constant phase element) and the resistance of the passive layer
2.1. Materials at the metal/electrolyte interface Qox and Rox respectively. These
parameters are related to the delamination of the coating. Qox is
Electrochemical impedance spectroscopy tests were carried out proportional to the delaminated area where a passive film is formed
on the Q-Panel cold rolled steel. The composition is summarized in during immersion in alkaline medium and thus increases with fil-
Table 1 [24]. iform corrosion and/or disbonding of the coating, Rox expressed
The steel samples (100 mm × 50 mm × 1 mm) were degreased in  decreases with the initiation and propagation of filiform
with acetone, immersed for 3 min at 60 ◦ C in a sodium hydroxide
solution at pH 12 and then rinsed with deionised water. The electro-
coating used is a commercial anticorrosion and toxic pigment free
(without lead) cataphoretic epoxy electrocoating supplied by PPG

Table 1
Chemical composition (weight %) of QPanel [24].

Weight (%)

Fe 98.10
Ma 0.25–0.60 max
C 0.13 max
P 0.04
S 0.05
Si 0.30
Ct 0.20
Cu 0.30
Fig. 2. Electrical equivalent circuit used to interpret the EIS data when the reactions
Balance 0.32
are controlled by charge transfer.
 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7 3

corrosion. Qox and Rox can only be determined when one time
constant is observed in the impedance spectra. This condition can
be approached when the dissolution of corrosion products due to
filiform corrosion is complete.
The Qox value can be only used to give a quantitative information
on the delaminated area if this parameter remains close to a pure
capacitance (n close to 1).

3. Results

3.1. Bare steel samples

3.1.1. Electrolyte
The effect of different parameters was investigated on bare steel
samples. First of all the choice of the electrolyte used to carry out
the EIS measurements was optimized. The passive behaviour of
steel was checked in alkaline solution at pH 12. The degreased steel
samples were immersed in 0.01 M NaOH solution (pH 12) and EIS
measurements were performed every half an hour. On the Bode dia-
grams (Fig. 3), only one time constant can be observed attributed
to the formation and properties of the passive layer. A reinforce-
ment of the passive behaviour of the oxide layer is observed during
the first hours of immersion and characterized by a more capaci-
tive behaviour at low frequencies. For longer immersion times than
17 h, the diagrams change with a loss of the capacitive behaviour
of the passive layer at low frequency. These changes are attributed
to the decrease of pH solution at value 11 with contact with the air.
In order to avoid this pH evolution, a commercial alkaline buffer
solution (di-sodium hydrogen phosphate/sodium hydroxide sup-
plied by VWR) was used. In Fig. 4, in the buffer solution at pH 12,
we can observe that the passive behaviour of steel appears for short Fig. 4. Bode modulus (a) and phase (b) diagrams for steel substrate immersed in
buffer alkaline solution at pH 12 after different immersion times.

immersion time and is stable with time. As a result, this electrolyte

was selected for determining the EIS spectra of scratched coated
steel samples.

3.1.2. Acid used to dissolve corrosion products

In order to reproduce the conditions of the filiform corrosion
initiation and select an appropriate acidic solution to dissolve the
corrosion products generated during the initiation period, the bare
steel samples were exposed for 1 h in HCl acid vapours as described
in the ISO/DIS 4623-1. After this step, the steel samples were
immersed, for different times between 15 s to 2 min, in acidic solu-
tions (sulfuric or hydrochloric acids at pH 1–3) in order to dissolve
the corrosion products formed during HCl vapor exposure. By opti-
cal observations, a cleanest surface is observed by using sulfuric
acid at pH 2 whatever immersion times.
In order to check the effect of the dissolution corrosion products
on the EIS diagrams obtained in the buffer alkaline solution, the
steel samples were exposed for 1 h in HCl acid vapor, the corrosion
products were dissolved in H2 SO4 aqueous solution at pH 2 for dif-
ferent immersion times (between 15 s and 2 min) and after rinsing
evaluated by EIS after 2 h 30 min of immersion in the buffer alkaline
solution at pH 12. On the Bode diagrams (Fig. 5(a) and (b)), if we
compare the results obtained for the different dissolution times in
sulfuric acid, similar Bode diagrams are observed.
The electrical equivalent circuit used for the numerical fitting
of the data is the same than shown in Fig. 2. In Table 2, the values
of Rox , Qox and n corresponding to the resistance and the non-ideal
capacitance of the passive layer respectively are determined for
the different immersion times in the acidic solution. These val-
ues do not change significantly with the immersion in the acidic
Fig. 3. Bode modulus (a) and phase (b) diagrams for steel substrate immersed in solution for the investigated period. The same behaviour of the pas-
NaOH at pH 12 after different immersion times. sive film on steel is observed by analysis in buffer alkaline solution
4 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7

Table 3
Results of the electrical parameters obtained by fitting for the scratched coated steel
placed for 1 h in HCl vapour and then dissolution of the corrosion products (2 min
in sulfuric acid solution at pH 2). EIS measurements in buffer alkaline solution at pH
12.

Time before EIS measurement Qox (Ss) Rox () n

30 min 6.4 × 10−6 8.3 × 105 0.9

1h 6.2 × 10−6 9.0 × 105 0.9
1 h 30 min 6.2 × 10−6 8.6 × 105 0.9
2h 6.4 × 10−6 8.0 × 105 0.9
2 h 30 min 6.4 × 10−6 8.0 × 105 0.9

The values of the Qox and Rox are practically constant till 2 h
30 min of immersion in the electrolyte.
Fig. 6 shows the EIS data obtained on scratched samples exposed
to the HCl vapour and placed for 0 h, 4 h and 24 h in climatic cham-
ber in order to propagate the filiform corrosion. The samples were
analyzed in buffer alkaline solution at pH 12 after 2 h 30 min of
immersion. Except for the sample not exposed to climatic cham-
ber, the EIS spectra show a complex phase diagram which cannot
be reduced to one single time constant. The behaviour is more resis-
tive in low and medium frequency ranges when exposure time to
the climatic chamber is increasing.
In order to explain this electrochemical behaviour, the EIS
response of the scratched electrocoated sample placed for 4 h in cli-
matic chamber was recorded in the buffer solution at pH 12 every
half an hour. On the Bode diagrams in Fig. 7a, after 30 min in con-
tact with the electrolyte, the value of the modulus at 0.01 Hz is low
and close to 104 . The phase angle is lower than 45 ◦ C in all the
investigated frequency range. With immersion time, the modulus
at low frequency is increasing and for immersion time longer than
Fig. 5. Bode modulus (a) and phase (b) diagrams for steel substrates for differ-
ent immersion times in sulfuric acid solution at pH 2. EIS measurements in buffer 1 h, two time constants are observed.
alkaline solution at pH 12 after 2 h 30 of immersion. This unstable EIS response behaviour can be explained as
described in the schematic representation shown in Fig. 8. The
after dissolution of the corrosion products formed during HCl vapor
exposure.

3.2. Electrocoated systems

The best conditions optimized on uncoated steel samples were

used to investigate the behaviour of scratched electrocoated steel
samples. The scratched samples were also submitted for 1 h in HCl
vapour to initiate filiform corrosion and exposed in the climatic
chamber for different periods. The dissolution of corrosion prod-
ucts was performed in H2 SO4 at pH 2. The EIS measurements were
performed in buffer solution at pH 12 after rinsing in deionised
water.
In order to check that immersion in the buffer alkaline solu-
tion does not induce a subsequent disbonding of the organic layer,
EIS spectra of the scratched coated samples were measured in this
solution as function of the immersion time. The capacitance and the
resistance of the passive layer in the defect are constant which leads
to the conclusion that the wet area is not modified by this immer-
sion period. The results obtained by using the electrical equivalent
circuit shown in Fig. 2 are presented in Table 3.

Table 2
Results of the electrical parameters obtained by fitting for the uncoated steel
substrate for different immersion times in sulfuric acid solution at pH 2. EIS mea-
surements in buffer alkaline solution at pH 12 after 2 h 30 min.

Steel substrate H2 SO4 Qox (Ss/cm2 ) Rox ( cm2 ) n

immersion time

Bare 15 s 4.0 × 10−5 1.4 × 105 0.92

2 h 30 min 30 s 4.1 × 10−5 1.0 × 105 0.92
Fig. 6. Bode modulus (a) and phase (b) diagrams for scratched electrocoated sam-
1 min 4.2 × 10−5 6.0 × 104 0.92
ples. Different times in climatic chamber and EIS measurements in buffer alkaline
2 min 4.0 × 10−5 3.2 × 105 0.92
solution at pH 12 after 2 h 30 of immersion.
 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7 5

Fig. 7. Bode modulus (a) and phase (b) diagrams for scratched electrocoated sam-
ples. 4 h in climatic chamber and EIS measurements every half an hour in buffer
Fig. 9. Bode modulus (a) and phase (b) diagrams for scratched electrocoated sam-
alkaline solution at pH 12.
ples. The potential is fixed at −1 V/OCP with different times of cathodic polarization.
EIS measurements in buffer alkaline solution at pH 12.
EIS spectra obtained for short immersion times are often observed
when a galvanic coupling is active [25]. In the first hour of
nated area more anodic. With time, corrosion products are forming
immersion in buffer alkaline solution, two different zones can be
and pH is becoming more uniform: two time constants are then
distinguished: a passive layer established in the scratch in direct
visible but new corrosion products are present under the delami-
contact with buffer solution and probably an active zone under-
nated coating. All these phenomena make the EIS spectra difficult
neath the delaminated coating where the pH does not reach a
to interpret and to be used to quantify the susceptibility to filiform
sufficient value to allow the formation of a passive layer. During the
corrosion of steel. In order to overcome the establishment of a gal-
first time of immersion, a galvanic coupling is created between this
vanic coupling a third step was included before EIS measurements
two zones: the scratch is probably more cathodic and the delami-
in alkaline solution. This step consists of submitting the scratched
sample to a short cathodic polarization in buffer alkaline solution.
During this step, the water reduction is strengthened and produced
gaseous hydrogen. This reaction will allow to homogenize fastly the
alkaline pH (production of hydroxyl ions) on all the metallic surface
and to facilitate the evacuation of corrosion products not dissolved
during the acidic dissolution step.
The parameters of the cathodic polarization must also be opti-
mized. The potential is fixed at −1 V vs OCP. The time between the
polarization and the EIS measurement is fixed at 10 min. Different
times of cathodic polarization comprised between 30 s and 3 min
were tested. The obtained results are presented in Fig. 9 for the
sample not submitted to climatic chamber. For this sample, delam-
ination is not present yet and so this sample is used to determine
the best compromise for the cathodic polarization time. As shown
on this diagram, for a time of the cathodic polarization higher than
1 min 30 s, two time constants are observed due to the degrada-
tion of the coating. In order to avoid a subsequent degradation of
the interface due to this step, the cathodic polarization time was
limited to 1 min.
In order to check the effect of the cathodic polarization after
delamination in climatic chamber, the same procedure was used
Fig. 8. Explanation of the unstable behaviour observed in the Bode diagrams in to evaluate the scratched electrocoated samples placed in climatic
Fig. 7. chamber for 4 h. EIS measurements were carried out every half
6 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7

Fig. 10. Bode modulus diagrams for scratched electrocoated samples. 4 h in climatic Fig. 12. Icat as a function of exposure time in climatic chamber. Experimental condi-
chamber, cathodic polarization (1 min at −1 V/OCP) and EIS measurement every half tions: scratched electrocoated steel sample, 2 min H2 SO4 pH 2, cathodic polarization
an hour in buffer alkaline solution at pH 12. (1 min at −1 V/OCP) and EIS measurements in buffer alkaline solution at pH 12 after
2 h 30 min.

an hour in buffer electrolyte solution at pH 12. In Fig. 10, a stable

behaviour is observed due to the evacuation of the corrosion the cathodic current at the end of the polarization time and the Rox
products and pH homogenization underneath the delaminated value determined by EIS in a buffer alkaline solution can be used
coating. In these conditions, one time constant is observed and to record the active area during corrosion as function of immersion
thus the exposed metallic area can be determined. time in climatic chamber. This value is a quantitative parameter to
Different exposure times in climatic chamber were tested after evaluate in short terms the extent of coating delamination or fili-
initiation of filiform corrosion by exposure to HCl vapour for 1 h: 0 h, form corrosion on steel. Nevertheless, this method presents some
6 h, 18 h and 24 h. By using the parameters defined by this study: limitations and is mainly useful to compare the sensitive to fili-
immersion in H2 SO4 pH 2 during 2 min for dissolving the corro- form corrosion in the initiation step and first hours of propagation.
sion products; cathodic polarization at −1 V OCP during 1 min for When filiform corrosion spreads with time, the procedure is not
pH homogenization and evacuation of remaining corrosion prod- sufficient elaborated to overcome the high tangential ohmic resis-
ucts; EIS measurements in buffer electrolyte solution at pH 12 after tance present in the filaments due to the incomplete dissolution
30 min. The diagrams show one time constant and the Rox values of the corrosion products. The correlation between charge trans-
can be determined by using the electrical circuit model used to fer resistance and delaminated area is lost after 24 h in climatic
interpret the EIS data of coatings with an artificial defect (Fig. 2). chamber. The real disbonded area should increase after this expo-
In Fig. 11, the Rox values (expressed in ) decrease with time in sure time although the resistance of the passive layer formed in
climatic chamber due to the increase of active area and thus to alkaline solution tends to a constant value (Fig. 11). The cathodic
the delamination or the filiform corrosion. The Qox value in that current shows the same tendency but seems to be a more sensitive
case cannot be used as a quantitative parameter to evaluate the parameter.
delaminated area because the n value decreases with the expo-
sure time in climatic chamber meaning that the behaviour can no 4. Conclusions
longer be considered as close to a pure capacitance. Fig. 12 also
shows that the cathodic current (expressed in ␮A) determined at EIS is useful to obtain quantitative data in short time (max. 24 h)
the end of the polarization time can also be used as a quantitative on susceptibility to delamination and filiform corrosion in compar-
value directly proportional to the exposed passive metallic area. ison with the normalized test (21 days).
This current increases with time in climatic chamber. Thanks to The sensitivity to filiform corrosion of steel covered by a
the optimization of the operating conditions, this study shows that cataphoretic coating was studied by electrochemical impedance
spectroscopy. The procedure used for investigating the steel sub-
strate takes into account that the equivalent circuit model used to
interpret the EIS data of coatings with an artificial defect is valid
if the corrosion products are correctly dissolved before charac-
terization. The steel is a very complex substrate and thus many
parameters must be optimized in order to remove the corrosion
products before EIS measurements. EIS measurements were car-
ried out in alkaline buffer solution at pH 12. The acid used to
dissolve the corrosion products is sulpfuric acid at pH 2. A short
cathodic polarization is necessary to evacuate corrosion products
and homogenize pH underneath the delaminated coating. The opti-
mization of the parameters leads to determination of resistance of
the passive film formed in alkaline solution before EIS measure-
ment and Icat value, two parameters which allow to quantify the
susceptibility to initiation and first hours of propagation of filiform
corrosion.
In the future, this procedure can be used to study the filiform
Fig. 11. Rox as a function of exposure time in climatic chamber. Experimental condi- corrosion for different grades of steel, pretreated steel, steel cov-
tions: scratched electrocoated steel sample, 2 min H2 SO4 pH 2, cathodic polarization
ered with different coatings (chemical composition, application,
(1 min at −1 V/OCP) and EIS measurements in buffer alkaline solution at pH 12 after
2 h 30 min.
thickness, etc).
 A.-P. Romano, M.-G. Olivier / Progress in Organic Coatings 89 (2015) 1–7 7

Acknowledgements [11] M.-G. Olivier, A.-P. Romano, C. Vandermiers, X. Mathieu, M. Poelman, Prog.
Org. Coat. 63 (2008) 323.
[12] T.M. Watson, A.J. Coleman, G. Williams, H.N. McMurray, Corros. Sci. 89 (2014)
This study was done in the framework of the Opti2mat and 46.
FLYCOAT “Programme Excellence” projects financed by the Région [13] A.-P. Romano, M.-G. Olivier, A. Nazarov, D. Thierry, Prog. Org. Coat. 66 (2009)
Wallonne, Belgium. The authors like to thank PPG, France for sup- 173.
[14] G. Bierwagen, D. Tallman, J. Li, L. He, C. Jeffcoate, Prog. Org. Coat. 46 (2003)
plying the cataphoretic bath. 148.
[15] M. Poelman, M.-G. Olivier, N. Gayarre, J.-P. Petitjean, Prog. Org. Coat. 54
(2005) 55.
References [16] M. Poelman, I. Recloux, N. Cornil, N. Blandin, L. Deronne, Y. Ledisert, M.-G.
Olivier, Prog. Org. Coat. 74 (3) (2012) 453–460.
[1] A. Bautista, Prog. Org. Coat. 28 (1996) 49. [17] M.-G. Olivier, M. Poelman, M. Demuynck, J.-P. Petitjean, Prog. Org. Coat. 52
[2] H.J.W. Lenderinck, Filiform Corrosion of Coated Aluminium Alloys (Ph.D. (2005) 263.
thesis), Delft University, 1995. [18] A.-P. Romano, M.-G. Olivier, C. Vandermiers, M. Poelman, Prog. Org. Coat. 57
[3] J.L. Delplancke, S. Berger, X. Lefèbvre, D. Maetens, A. Pourbaix, N. Heymans, (2006) 400.
Prog. Org. Coat. 43 (2001) 64. [19] A. Nazarov, A.-P. Romano, M. Fedel, F. Deflorian, D. Thierry, M.-G. Olivier,
[4] C. Sharman, Nature 153 (1994) 621. Corros. Sci. 65 (2012) 187.
[5] A. Afseth, J.H. Nordlien, G.M. Scamans, K. Nisancioglu, Corros. Sci. 44 (2002) [20] L. Fedrizzi, F. Deflorian, S. Rossi, Benelux Metall. 37 (1997) 243.
2491. [21] L. Fedrizzi, F. Deflorian, S. Rossi, P.L. Bonara, Mater. Sci. Forum 289–292 (1998)
[6] J.H.W. de Wit, Electrochem. Acta 46 (2001) 3641. 485.
[7] P.P. Leblanc, G.S. Frankel, J. Electrochem. Soc. 151 (2004) B105. [22] S.E. Frers, M.M. Stefenel, C. Mayer, T. Chierchie, J. Appl. Electrochem. 20
[8] J.-S. Han, J.-H. Park, Corros. Sci. 46 (4) (2004) 787. (1990) 996.
[9] A.P. Kayes, JCSE 2 (1999) 1. [23] M. Pourbaix, Atlas d’equilibres électrochimiques, Gauthier-Villars, Paris, 1963.
[10] A. Afseth, G.M. Scamans, 5th Aluminium Chair, Aluminium for its Functional [24] Qpanel “Panneaux test normalisés” Lab Products, Document du 01.12.2012.
Surface Properties, 27th of March 2002, Brussels, 2002. [25] M. Olivier, A. Lanzutti, C. Motte, L. Fedrizzi, Corros. Sci. 52 (2010) 1428.