Corrosion Science 47 (2005) 937–951

www.elsevier.com/locate/corsci

EIS characterisation of anodic films formed

on 2024 aluminium alloy, in sulphuric acid
containing molybdate or permanganate species
V. Moutarlier a, M.P. Gigandet a,*
, B. Normand b, J. Pagetti a

a
Laboratoire de Chimie des Materiaux et Interfaces (LCMI), Equipe Corrosion et
Traitements de Surface, 16 Route de Gray, 25 030 Besançon Cedex, France
b
LPLE, UPR15-CNRS, Université P. et M. Curie, Paris VI, 4 Place Jussieu,
75 252 Paris Cedex 05, France

Received 23 May 2003; accepted 21 June 2004

Available online 22 September 2004

Abstract

Electrolytes composed of sulphuric acid and corrosion inhibitors (molybdate or permanga-

nate species) were proposed in order to replace chromic acid for the anodising of 2024 alumin-
ium alloy. The electrochemical impedance spectroscopy (EIS) method was used to visualise the
correlation between the corrosion performance in NaCl and the morphology of these new ano-
dic layers. From an appropriate equivalent circuit, EIS parameters concerning the porous and
barrier layers were detected. Their evolution during corrosion tests was discussed. The results
indicate that the morphology and the corrosion resistance of anodic films formed in acid sul-
phuric with molybdate species remain unchanged. On the contrary, morphological properties
of anodic films formed in presence of permanganate species are modified, favouring their cor-
rosion performance. EIS analyses were completed with SEM technique.

2004 Elsevier Ltd. All rights reserved.

Keywords: A. Aluminium alloy; B. Anodising; B. Sealing; B. Electrochemical impedance spectroscopy

(EIS); C. Corrosion inhibitor

*
Corresponding author. Tel.: +33 3 81 662030; fax: +33 3 81 662033.
E-mail address: marie-pierre.gigandet@univ-fcomte.fr (M.P. Gigandet).

0010-938X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.06.019
938 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

1. Introduction

The anticorrosive properties of aluminium and its alloys are strongly increased by
the anodising process. Application of an anodic potential to aluminium sample im-
mersed in an appropriate electrolyte causes oxide growth [1–4]. In electrolytes such
as sulphuric acid and chromic acid, anodic layers are known to present a duplex
structure: a thin non-porous compact layer called the barrier layer and an outer por-
ous layer. The porous layer is composed of hexagonal cells in a honeycomb arrange-
ment. A cell has a central pore normal to the metal substrate. Porous layer is usually
about 103–104 times thicker than barrier layer. Moreover, the corrosion resistance of
porous anodic layers is enhanced by an hydrothermal treatment called sealing. Seal-
ing process achieves an important reduction in the porosity of the anodic layer.
In order to replace hexavalent chromium in anodising process (chromic acid as
electrolyte), several studies have been realised [5–8]. Our laboratory proposes a
mixed bath containing sulphuric acid and corrosion inhibitors [9]: molybdate ions
or permanganate ions. Anodising in sulphuric acid containing molybdate or perman-
ganate species has shown modifications on anodic film formation [10]. Oxide film
formation has been hindered with molybdate ions. On the contrary, oxide film
growth in presence of permanganate ions has been promoted, probably due to
their oxidising power. The first corrosion data have shown an improvement for
the anodic film formed with permanganate, close to those obtained for chromic ano-
dic films [9].
In this situation, it is interested to study, in details, corrosion performance of the
anodic layers formed in sulphuric acid containing molybdate or permanganate ions.
The application of electrochemical impedance spectroscopy (EIS) to characterise
corrosion resistance of porous oxide films has many advantages [11,12]. EIS meas-
urements allow to characterise the barrier layer properties and, with sealing, the por-
ous layer properties. EIS measurements can follow the degradation of oxide films in
an aggressive medium. From appropriate electrical equivalent circuits, representative
parameters of corrosion process can be extracted. Therefore, this research has corre-
lated the morphology of these new anodic layers to their corrosion behaviour in
NaCl solution determined by EIS.

2. Experimental procedure

2.1. Anodising and sealing

Samples of aluminium alloy 2024 T3 (wt.%: 4.45 Cu, 1.51 Mg, 0.63 Mn, 0.17 Fe,
0.08 Zn, 0.06 Si, 0.01 Cr, 0.03 Ti) were used. Before anodising, samples were de-
greased in a commercial alkaline cleaner at 60 C for 20 min, dipped in an alkaline
solution (NaOH 50 g L
1) at 45 C for 1 min and neutralised in a sulphuric/chromic
mixture (H2SO4: 200 g L
1, CrO3: 50 g L
1) for 30 s at room temperature. In the
future, this last step should be replaced (pre-treatment without Cr VI [6,7]). After
each step, samples were rinsed in distilled water and air dried.
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 939

Anodising process was performed for 20 min, under 1 mA cm
2, at 20 C. Different
electrolytes were employed:

• a sulphuric acid solution (18 wt.%),

• a sulphuric acid containing 0.1 M of Na2MoO4 (purity: 99.5%),
• a sulphuric acid containing 0.1 M of KMnO4 (purity: 99.0%).

Few anodised samples were sealed. This treatment was carried out in boiling distilled
water for 30 min. After sealing, samples were air dried.
The morphology of anodic layers was investigated using a scanning electron
microscope (SEM), with a JEOL JSM 5600 model.

2.2. Electrochemical impedance spectroscopy (EIS)

The classical three-electrode configuration was used. An anodised sample as

working electrode with an exposed area of 8 cm2, a saturated calomel electrode as
reference electrode and a platinum sheet as auxiliary electrode were employed.
The test solution was a NaCl solution (5 wt.%) and the electrochemical cell was kept
at 35 ± 2 C, open to air. Impedance tests were realised 2 days after anodising/sealing.
The equipment was a Solartron 1255 Frequency Response Analyser connected to the
cell via a PAR 273 Potentiostat. Impedance measurements were conducted over a
frequency range of 105 down to 10
2 Hz, with eight points per decade, using a
10 mV (rms) sin wave. Samples were tested at different periods of immersion: 1, 2,
10, 24 and 48 h. Data were presented as Nyquist plots. The results were analysed
using the fit program Equivcrt (impedance data analysis system, B.A. Boukamp Uni-
versity of Twente, Netherlands). This software uses an electrical circuit composed of
a resistance R0 in series with a resistance R1 and a capacitance C1 (with its frequency
dispersion factor aðC1 Þ ) in parallel.

3. General model

As mentioned in introduction, the aluminium oxide film consists of a very thin

compact part and a thick porous part. In order to describe the electrochemical
behaviour of this system, both oxide parts are considered independent and separated
into two oxide phases: porous and barrier parts. Moreover, the porous part is com-
posed of pores and walls of hexagonal cells. According to previous studies [13–17],
the properties of each part can be characterised by resistances and capacitances, in
parallel and in series, describing their electronic and dielectric behaviours. Since
the pioneering work of Hoar and Wood [13], various equivalent circuits have been
proposed to model the response of porous anodic films. It is accepted that the porous
anodic film can be modelled by the equivalent circuit proposed by Hitzig et al. [15]
and presented in Fig. 1a. This model is successfully applied to explain the properties
of the barrier and porous parts [18,19].
940 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

(a)

Rel

i) ii) Rel : electrolyte resistance

Rw : hexagonal cells resistance
Rw Cw Cw : hexagonal cells capacitance
Rp : electrolyte resistance through pores
Cp : electrolyte capacitance through pores
Rp Cp Rb : barrier layer resistance
Cb : barrier layer capacitance

iii)

Rb Cb i) wall of hexagonal cells

ii) porous layer : pores
iii) barrier layer

(b)

Rel

Rp Cp

Rb Cb

Fig. 1. Equivalent circuits to model the impedance behaviour of anodised aluminium films. (a) General
model and (b) simplified model.

In this model, Rel is the electrolytic resistance, i.e. NaCl solution. Rel is low with
about 15 X cm2.
One of the parallel branches in the circuit is formed by the resistance Rw and the
associate capacitance Cw. They represent the walls of the hexagonal cells. Rw and Cw
are generally omitted since they are extremely high and extremely low, respectively.
Indeed, the walls of hexagonal cells prevent the passage of current. In this way,
equivalent circuit can be reduced to that illustrated in Fig. 1b.
Therefore, parameters concerning the porous layer are associated to the pores and
characterised by the capacitance Cp and the resistance Rp. Barrier layer properties
are described by the capacitance Cb and the resistance Rb. However, porous and bar-
rier layers have heterogeneities making their capacitive behaviour better simulated
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 941

by constant phase elements (CPE), than by simple capacitances, C [CPE = 1/C(jx)a].

Thus, parameters aðCb Þ and aðCp Þ are affected to Cb and Cp, respectively, to take into
account the non-ideal capacitive behaviour [16]. The parameter a is the frequency
dispersion factor and varies from 1 to 0. Only in the case where a = 1, Cb and Cp
can be considered as real capacitances.

4. Impedance characteristics of unsealed anodic films

4.1. Impedance diagrams for unsealed anodic films

Fig. 2 reports the evolution of impedance diagrams vs. immersion time in a NaCl
solution, for the unsealed anodic layers formed in sulphuric, sulphuric/molybdate
and sulphuric/permanganate media. For unsealed anodic layers, porous layer prop-
erties could not be detected due to the high conductivity of the electrolytic solution
inside the pores. Therefore, only one capacitive arc is observed in the low frequen-
cies. Previous studies have shown that this corresponds to the characteristics of bar-
rier layers [13–15]. So, the parameters used to describe the electrochemical behaviour
of unsealed anodic films are Rb, Cb as CPE with aðCb Þ . The parameters Cb with aðCb Þ
are presented in Table 1 and the Rb values in Fig. 3, as a function of immersion time.

4.2. Immersion time: 1 h

With the high dispersion of data at low frequencies, the estimation of Rb values is
uncertain. However, the initial Rb values are 107 X cm2, in average. These results are
relatively consistent with the value proposed in the literature (Rb = 107 X cm2 [19],
Rb = 109 X cm2 [20]). At 1 h, the resistance Rb for the anodic film formed with per-
manganate is the highest with 2 · 107 X cm2. At the same time, the Rb values for
the anodic films formed in sulphuric acid without and with molybdate are similar
and lower with about 9 · 106 X cm2.
It is known that the capacitance Cb can be connected with the barrier layer thick-
ness eb, by the relation: Cb = er Æ eo Æ S/eb (1), where eo = 8.85 · 10
14 F cm
1 is the die-
lectric constant in vacuum, er = 10 is the relative constant for alumina and S = 8 cm2
is the electrode surface [14]. The relation (1) is acceptable if aðCb Þ is close to 1 [16],
when the CPE is close to an ideal capacitance, i.e. essentially at 1 h of immersion
(see Table 1). This corresponds to a barrier layer relatively homogeneous. Thus, at
1 h of immersion, Cb values are connected to barrier layer thicknesses eb. For anodic
films formed in sulphuric acid, eb is 15 nm (value calculated with the relation (1)).
For anodic films formed with molybdate and permanganate, eb are 15 and 18 nm,
respectively. Permanganate addition into sulphuric acid seems to increase barrier
layer thickness. This explains why Rb value is the highest for this anodic film: the
barrier layer becomes more resistant against electrolyte penetration.
The parameter aðCb Þ takes into account the non-ideal capacitive behaviour of bar-
rier layers [16]. Barrier layers are heterogeneous. Indeed, barrier layers can be mod-
ified in composition and in morphology, essentially by the incorporation of alloying
942 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

600000 1h
2h 6000
10 h
24 h

400000 48 h
4000
Ω .cm²

Ω .cm²
200000 10 Hz 1 Hz
1 Hz 2000

0 0
0 200000 400000 600000 Zoom 0 2000 4000 6000
(a) Ω .cm² Ω .cm²

600000 6000
1h
2h
10 h

400000 24 h
4000
48 h
Ω .cm²

Ω .cm²

10 Hz
1 Hz
1 Hz
200000 2000

0 0
0 200000 400000 600000 0 2000 4000 6000
(b) Ω .cm² Zoom Ω .cm²

600000 6000

1 Hz
400000 4000
Ω .cm²

Ω .cm²

10 Hz
0.1 Hz 1h
2h
200000 2000
10 h
24 h
1 Hz 48 h

0 0
0 2000 4000 6000
0 200000 400000 600000 Zoom
(c) Ω .cm² Ω .cm²

Fig. 2. Nyquist plots as a function of exposure time, in NaCl solution, for the unsealed anodic films
formed in (a) sulphuric, (b) sulphuric/molybdate and (c) sulphuric/permanganate media.

elements (Cu, Mg, Mn, . . .) [21]. This alters their homogeneity. Initially, aðCb Þ
values are close to 1 (Table 1). Only few defects due to alloying elements seem to
be present.
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 943

Table 1
Electrochemical parameters (Cb and aðCb Þ ) as a function of immersion time, for the unsealed anodic films
formed in sulphuric, sulphuric/molybdate and sulphuric/permanganate media
Sulphuric With molybdate With permanganate
Cb (lF/cm2) aðC b Þ Cb (lF/cm2) aðCb Þ Cb (lF/cm2) aðC b Þ
1h 0.6 0.91 0.6 0.92 0.5 0.95
2h 1.3 0.89 1.2 0.90 1.0 0.95
10 h 3.8 0.77 3.2 0.88 2.8 0.91
24 h 8.7 0.78 7.9 0.76 5.6 0.88
48 h 10.2 0.68 9.8 0.71 7.8 0.77

1E+08
sulphuric
1E+07 molybdate
Rb ( Ω.cm²)

permanganate
1E+06
Rb + Rcorr
1E+05

1E+04

1E+03
0 10 20 30 40 50
Time (h)

Fig. 3. Variation of Rb as a function of immersion time for the unsealed anodic films formed in sulphuric,
sulphuric/molybdate and sulphuric/permanganate media.

4.3. Immersion time: from 2 to 48 h

From 2 to 24 h, the electrolyte penetrates easily through porous layers to attack

barrier layers. Indeed, Cb values increase with immersion time resulting of the deg-
radation of barrier layers with the decrease of their thickness. So, barrier layers res-
istances decrease with immersion time. The decrease of aðCb Þ with exposure time
indicates an increase of flaws due to the electrolyte penetration, amplifying the
heterogeneity.
After 24 h, Cb values are very high (5 lF/cm2), aðCb Þ values are close to 0.70 and
Rb values are low (104 X cm2). This shows a strong degradation of barrier layers.
Indeed, after 24 h, pits are effectively visualised in unsealed anodic films. Pit forma-
tion can be located on Nyquist plots. Indeed, in Fig. 2, the surrounded deformations
translate the pit growth. Deformations can be associated with the apparition of a
second loop in the capacitive loop at the low frequencies.
Moreover, the evolution of Cb, aðCb Þ and Rb values with immersion time shows the
best performances for the anodic film formed with permanganate. The initial barrier
layer thickness is effectively the thickest for this anodic film (18 nm instead of 15 nm),
improving its resistance against electrolyte penetration.
944 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

Rel

Rb/θ θ.Cb Rel : electrolyte resistance

Rb : barrier layer resistance
Cb : barrier layer capacitance
Rcorr/(1-θ) (1- θ).Cdl
θ : fraction of substrate covered by anodic film
Rcorr : corrosion resistance of substrate
Cdl : double layer capacitance of substrate

Fig. 4. Equivalent circuit to model the electrolyte penetration though the unsealed anodic film.

4.4. Equivalent circuit for unsealed anodic films

As porous layer properties are not detected for unsealed anodic films, the equiv-
alent circuit in Fig. 1 can be reduced to the very simple model with Rel, Rb and Cb.
Deformations, after 24 h of immersion, at the low frequencies on the impedance
diagrams, require modification of the model. New parameters can be introduced
in the very simple model, to symbolise the electrolyte penetration through the barrier
layer to attack the substrate. So, the parameter h represents the fraction of the alu-
minium surface covered by the anodic layer, the parameter Rcorr is the corrosion
resistance of the aluminium substrate and the parameter Cdl corresponds to the dou-
ble layer capacitance of the substrate. The modified model with these new parame-
ters is presented in Fig. 4 [15,22].
For h = 1, the barrier layer is not damaged. The aluminium alloy surface is en-
tirely covered by the barrier layer. This corresponds to 1 h of immersion. Parameters
Rcorr and Cdl do not exist. Only Rb and Cb with aðCb Þ values are detected.
When h is close to 1, this translates the attack of the barrier layer, i.e. immersion
time from 2 h to 24 h. Parameters Rcorr and Cdl remain too weak to be determined.
With the immersion time, h decreases and the aluminium alloy surface becomes
uncovered by a continuous barrier layer. The substrate is attacked and pits appear,
i.e. after 24 h of immersion. So, at low frequencies, two capacitive loops are visible
corresponding to Rb with Cb and Rcorr with Cdl parameters. It is difficult to distin-
guish Rb from Rcorr and Cb from Cdl (see Fig. 3).
For h close to 0, only Rcorr and Cdl could be detected (time higher than 48 h of
immersion).

5. Impedance characteristics of sealed anodic films

5.1. Impedance diagrams for sealed anodic films

Fig. 5 reports the evolution of impedance diagrams vs. immersion time in a NaCl
solution, for the sealed anodic layers formed in sulphuric, sulphuric/molybdate and
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 945

6000000 10000
Part a 1h Part b
2h
10 h 500
4000000
100 Hz

Ω .cm²
Ω .cm²

24 h
0.1 Hz 5000
48 h 250

2000000 1000 Hz
0
Zoom 0 250 500

0
0
0 2000000 4000000 6000000 0 5000 10000
(a)
Ω .cm² Ω .cm²

6000000 10000
Part a 1h Part b
2h
10 h
4000000
24 h
Ω .cm²

500
Ω .cm²

100 Hz
48 h 5000
0.1 Hz
250
2000000
1000 Hz
0
Zoom 0 250 500
0 0
0 2000000 4000000 6000000
0 5000 10000
(b) Ω .cm² Ω .cm²

6000000 1h 10000

Part a 2h
Part b
10 h
24 h
4000000
Ω .cm²
Ω .cm²

48 h
0.1 Hz 5000

2000000

1000 Hz
0
0 0 5000 10000
0 2000000 4000000 6000000 Ω .cm²
(c) Ω .cm²

Fig. 5. Nyquist plots as a function of exposure time in NaCl solution for the sealed anodic films formed in
(a) sulphuric, (b) sulphuric/molybdate and (c) sulphuric/permanganate media. Part a: Low frequencies.
Part b: High frequencies.

sulphuric/permanganate media. The main reaction of sealing process is the blockage

of pores due to the formation of hydrated alumina, probably boehmite (AlO(OH))
[23]. After sealing, Nyquist plots are modified and characterised by the presence of
two capacitive loops. Several studies have already shown that the low frequency
range corresponds to the barrier layer properties (Part a) and the high and medium
frequency ranges reflect the sealed porous layer properties (Part b) [13–15,20,24].
Therefore, sealing process that is ascribed to pore closure allows to detect porous
layer properties. So, parameters to describe the electrochemical behaviour of sealed
anodic films are Rp, Cp with aðCp Þ , Rb and Cb with aðCb Þ .
946 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

5.2. Barrier layer characteristics

Barrier layer characteristics are determined from the low frequencies of Nyquist
plots (Part a in Fig. 5). Table 2 reports the evolution of Cb and aðCb Þ with exposure
time. Fig. 6 shows the variation of Rb as a function of immersion time.
Sealing modifies barrier layer properties. Indeed, Cb values are lower and Rb val-
ues are higher for sealed anodic films (comparison Tables 1 and 2, Figs. 3 and 6).
Hoar and Wood suggest that sealing consists of a general reduction of sectional area
of each pore with the formation of a ‘‘plug’’ in the pore bottom [2,13]. This pheno-
menon is illustrated in Fig. 7. Therefore, the Cb decrease corresponds to the increase
of the barrier layer thickness. This improves its resistance against the electrolyte pen-
etration, so Rb values are higher. Consequently, the arrival of aggressive ions in the
vicinity of the barrier layer, where they attack the substrate, is slowed down. No pits
are observed after 48 h of immersion. No deformations at low frequencies in Nyquist
plots are visualised.
The values aðCb Þ are also more important after sealing. Sealing can ‘‘plug’’ the
flaws present in barrier layers, increasing the homogeneity.

Table 2
Electrochemical parameters (Cb and aðCb Þ ) as a function of immersion time, for the sealed anodic films
formed in sulphuric, sulphuric/molybdate and sulphuric/permanganate media
Sulphuric With molybdate With permanganate
Cb (lF/cm2) aðCb Þ Cb (lF/cm2) aðC b Þ Cb (lF/cm2) aðCb Þ
1h 0.5 0.94 0.5 0.95 0.2 0.98
2h 1.0 0.92 1.0 0.92 0.4 0.95
10 h 2.1 0.92 1.2 0.90 0.8 0.92
24 h 3.2 0.86 2.8 0.88 1.8 0.88
48 h 3.9 0.82 3.4 0.81 2.4 0.87

1E+08

1E+07
Rb ( Ω.cm²)

1E+06

1E+05 sulphuric
molybdate
1E+04
permanganate
1E+03

1E+02
0 10 20 30 40 50
Time (h)

Fig. 6. Variation of Rb as a function of immersion time for the sealed anodic films formed in sulphuric,
sulphuric/molybdate and sulphuric/permanganate media.
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 947

0
I
II
III

Fig. 7. Schematic representation of sealing process. Stage 0: Wall of unsealed pore. Stages I–III:
Successive stages of sealing.

In any case, impedance data for sealed barrier layers are in good agreement with
impedance responses for unsealed barrier layers: molybdate addition improves
weakly corrosion resistance whereas permanganate addition increases strongly cor-
rosion performance. The barrier layer thickness for the anodic film formed with per-
manganate is effectively the thickest.

5.3. Porous layer characteristics

Porous layer characteristics are determined from the high frequencies of Nyquist
plots (Part b in Fig. 5). Evolutions of Cp, aðCp Þ and Rp parameters as a function of
immersion time are reported in Table 3 and in Fig. 8.

5.3.1. Immersion time: 1 h

The parameter Cp (Table 3) is associated to the capacitive behaviour of the pore
filling, in parallel to the hexagonal cell walls. Cp depends principally on the oxide
roughness, but not on the porous layer thickness [16]. Cp value is higher for anodic
films formed in sulphuric and in sulphuric/molybdate media than for film formed
with permanganate. The oxide roughness (porosity in surface) is probably the smoo-
thest for the anodic film formed with permanganate. Micrographs, in Fig. 9, confirm

Table 3
Electrochemical parameters (Cp and aðCp Þ ) as a function of immersion time, for the sealed anodic films
formed in sulphuric, sulphuric/molybdate and sulphuric/permanganate media
Sulphuric With molybdate With permanganate
2 2
Cp (lF/cm ) aðC p Þ Cp (lF/cm ) aðCp Þ Cp (lF/cm2) aðC p Þ
1h 0.9 0.89 0.8 0.90 0.2 0.92
2h 1.1 0.87 0.9 0.87 0.5 0.91
10 h 2.3 0.82 2.0 0.83 0.7 0.90
24 h 3.2 0.76 2.8 0.78 0.9 0.88
48 h 3.8 0.60 3.2 0.71 1.1 0.82
948 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

30000 sulphuric
molybdate
25000 permanganate
20000
Rp (Ω .cm²)
15000
10000
5000
0

0 10 20 30 40 50
Time (h)

Fig. 8. Variation of Rp as a function of immersion time for the sealed anodic films formed in sulphuric,
sulphuric/molybdate and sulphuric/permanganate media.

that porosities of anodic layers formed in sulphuric and sulphuric/molybdate media

are effectively the most pronounced. For sulphuric/permanganate film, pores in sur-
face appear smaller and the oxide surface less rough.
The parameter aðCp Þ (Table 3) takes into account the non-ideal capacitive behav-
iour of porous layers. As the initial aðCp Þ values are far from 1, the heterogeneity of
porous layers seems important. Porous layers are modified in composition and in
morphology. Indeed, they are contaminated by species derived from substrate (alloy-
ing elements) [22] and from electrolyte such as sulphate ions (from sulphuric acid)
[9]. Moreover, porous layers are strongly disorganised. Pores are not unidirectional;
they grow in all direction as we can see in Fig. 9. This disorganisation has already
been observed for anodic film formed on Al 2024 [18,25].
The parameter Rp (Fig. 8) is easily determined in the high frequencies from Fig. 5.
Porous layer resistances are lower than the associate barrier layer resistance values.
Indeed, sealed pores remain much better conductor than barrier layers. The initial Rp
for the anodic film formed with permanganate is higher than Rp values for other
anodic films. In this case, the porosity is effectively the lowest and the porous layer
thickness the highest (see Fig. 9). So, this porous layer is more resistant against elec-
trolyte penetration.

5.3.2. Immersion time: from 2 to 48 h

For all anodic films, Cp values increase and Rp values decrease with exposure
time, showing the penetration of the electrolyte through porous layers. Evolution
of Cp and Rp is the slowest for the anodic layer formed in presence of permanganate.
A more rapid evolution is observed for the anodic films formed in sulphuric and
sulphuric/molybdate media, showing an easier electrolyte penetration. It can be
attributed to the increase of the porous layer thickness and the decrease of porosity
for the anodic films formed with permanganate. These factors slow down the electro-
lyte penetration through the porous layer.
The aðCp Þ values decrease with immersion time indicating an increase of the heter-
ogeneity due to the electrolyte penetration through porous layers. As the electrolyte
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 949

Fig. 9. Micrographs (SEM), surface and section of the anodic layers formed in (a) sulphuric, (b) sulphuric/
molybdate and (c) sulphuric/permanganate media.

penetration is the weakest for the anodic film formed with permanganate, the aðCp Þ
decrease is the slowest.

5.4. Equivalent circuit for sealed anodic films

From these data, the equivalent circuit for sealed anodic films is proposed in Fig.
10. With sealing, parameters of porous layer are detected (Rp and Cp with aðCp Þ ).
Parameters concerning barrier layer are also presented (Rb and Cb with aðCb Þ ).
According to the model of Fig. 4, the new parameters h, Rcorr and Cdl are introduced
950 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951

Rel

Rel : electrolyte resistance

Rp : electrolyte resistance through pores
Rp/θ θ.Cp Cp : electrolyte capacitance through pores
Rb : barrier layer resistance
Rcorr/(1-θ) (1-θ).Cdl Cb : barrier layer capacitance
θ : fraction of substrate covered by anodic film
Rb/θ θ.Cb Rcorr : corrosion resistance of substrate
Cdl : double layer capacitance of substrate

Fig. 10. Equivalent circuit to model the electrolyte penetration though the sealed anodic film.

to symbolise the electrolyte penetration through the porous layer and the barrier
layer [14].
The parameter h corresponds to the fraction of the substrate surface covered by
the anodic film. For h = 1, the porous and barrier layers are not damaged. The alu-
minium alloy surface is entirely covered by the anodic film. This corresponds to 1 h
of immersion. Parameters Rcorr and Cdl do not exist.
When h is close to 1, this translates the attack of the porous layer and then of the
barrier layer, i.e. immersion time from 2 h to 48 h. Parameters Rcorr and Cdl are too
weak to be determined. However, no pits have been observed at 48 h of immersion
for sealed anodic films. So, under these conditions h is not close to 0. In this case,
corrosion parameters (Rcorr and Cdl) remain undetectable.

6. Conclusions

The corrosion performance of anodic layers formed in sulphuric, sulphuric/

molybdate and sulphuric/permanganate media has been studied by EIS, in NaCl
solution. The EIS measurements have offered the possibility to follow the corrosion
process.
At first, electrolyte has easily penetrated through unsealed porous layers and with
difficulty through sealed porous layers. Sealing has improved corrosion resistance by
closing pores and has allowed to detect porous layer parameters.
Then, electrolyte has penetrated through barrier layers. The electrolyte attack has
been hindered after sealing. This treatment has strongly improved corrosion resist-
ance by increasing barrier layer thickness. Thus, only without sealing, pit formation
has been visualised.
Moreover, this research has shown a strong correlation between the morphology
of anodic layers and the corrosion performance. As the morphology of the anodic
films formed with molybdate ions was weakly modified, the corrosion resistance
has remained close to those formed in sulphuric acid without additives. On the con-
trary, permanganate addition has changed the morphology (reduction of porosity,
 V. Moutarlier et al. / Corrosion Science 47 (2005) 937–951 951

increase of porous and barrier layers thicknesses). These anodic layers have pre-
sented the best corrosion performance.
Morphology of anodic films is an important factor to explain corrosion process.
An other parameter must be elucidated: corrosion mechanisms due to inhibitors
incorporated into anodic films.

Acknowledgements

Authors acknowledge the ‘‘LPLE, UPR15-CNRS, Université P. et M. Curie,

Paris VI, France’’ where SEM photographs were made.

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