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Corrosion protection of clad 2024 aluminum alloy anodized in tartaric-

sulfuric acid bath and protected with hybrid sol–gel coating

Article in Electrochimica Acta · April 2014

DOI: 10.1016/j.electacta.2013.09.004

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 Electrochimica Acta 124 (2014) 69–79

Contents lists available at ScienceDirect

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

Corrosion protection of clad 2024 aluminum alloy anodized in

tartaric-sulfuric acid bath and protected with hybrid sol–gel coating
V.R. Capelossi a,b , M. Poelman c , I. Recloux a , R.P.B. Hernandez b ,
H.G. de Melo b , M.G. Olivier a,c,∗
a
Faculty of Engineering, University of Mons, 20, Place du Parc, Mons, Belgium
b
Polytechnic School of the University of São Paulo, Av. Prof. Luciano Gualberto, Trav. 3, n◦ 380, CEP 05508-010, São Paulo, SP, Brazil
c
Materia Nova Research Centre, 1, Avenue N. Copernic, Parc Initialis, Mons, Belgium

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

Article history: Clad AA2024 T3 specimens were anodized in a tartaric-sulfuric acid bath (TSA) and subsequently pro-
Received 4 February 2013 tected either by classical Cr-free water sealing treatment or by application of a hybrid sol–gel coating.
Received in revised form 3 September 2013 The sol–gel coating was prepared using a solution with high water content (58 %v/v) and obtained by
Accepted 4 September 2013
the hydrolysis and condensation of tetraethoxysilane (TEOS) and 3-glycidoxypropyltrimethoxysilane
Available online 14 September 2013
(GPTMS). The morphology of the sealed anodic films and their thicknesses were evaluated by scanning
electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM) and glow discharge
Keywords:
optical emission spectrometry (GDOES). The corrosion resistance of the samples was evaluated by elec-
AA2024-T3
Anodizing process
trochemical impedance spectroscopy (EIS) and salt-spray test. The results showed that the treatment
Sealing with the hybrid sol–gel increased the resistive properties of the pores compared to the classical water
Hybrid sol–gel coatings sealing, delaying the access of aggressive species to the barrier layer.
Corrosion protection © 2013 Elsevier Ltd. All rights reserved.

1. Introduction corrosion resistance to the whole system, as proved in several pub-

The 2xxx aluminum alloys are frequently used in the aircraft
industry due to their high specific strength and light weight [1].
These alloys contain elements, as copper, used to improve their
mechanical properties. However, copper rich intermetallics form
microscopic galvanic couples which make these materials very
sensitive to corrosion. To prevent the onset of localized corrosion
processes that could impair the mechanical performance of the
built structures the most common practice is to avoid the direct
contact of the electrochemically active matrix with the surround-
ing environment by applying a protective coating system. In order
to extend the service life of the parts, in the aircraft industry, prior
to painting application, the basis matrix is frequently cladded or
anodized.
The corrosion protection afforded by Alclad products relies in
two basic principles. Initially the cladding material must be anodic
in comparison with the base metal [2], providing cathodic protec-
tion to this latter in case of severe corrosion damage. In addition
the microstructure of the cladding material must exhibit a lower
number of intermetallic particles [3], providing superior localized
∗ Corresponding author at: Faculty of Engineering, University of Mons, 20, Place
du Parc, Mons, Belgium. Tel.: +32 65374431; fax: +32 65374416.
E-mail address: marjorie.olivier@umons.ac.be (M.G. Olivier).
lished scientific works [3–5].
Anodization is based on the growth of an Al oxide layer by apply-
ing anodic potentials. This treatment gives rise to a duplex structure
composed of a porous layer, comprising a close-packed array of
hexagonal columnar cells perpendicular to the substrate, and a
thin compact barrier layer in contact with the substrate [6]. The
chromic acid anodizing process is the most widely used to produce
these layers providing excellent corrosion protection [7]. This treat-
ment can be used before painting without sealing post-treatment
thanks to Cr(VI) self-healing ability. Furthermore, the roughness of
the unsealed layer favors paint adhesion. Nevertheless, due to toxi-
cological and environmental problems associated with hexavalent
chromium, a range of developments on the production of Cr(VI)-
free anodization baths has emerged in recent years. Researchers
have mainly focused on the replacement of chromic acid anodizing
by sulfuric acid anodizing (SAA) without [8–10] or with [5,11–15]
the addition of modifiers. One of such modifier is tartaric acid
[5,12–14,16,17], which, like other organic acids [18–21], seems to
be able to produce anodic aluminum films with self-ordered poros-
ity [17,22].
In the aircraft industry, whenever anodized Al alloys are
used in service, the layer must be either painted or sealed. This
latter process is frequently carried out by immersion in hot
aqueous potassium dichromate solution. In order to completely
remove Cr(VI) from the process, anodic films produced from

0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.09.004
70 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79
tartaric-sulfuric anodizing (TSA) baths have been frequently sealed
by immersion in boiling water [12]. Several works have shown that
hydrothermally sealed anodic films produced on 2xxx Al alloys
from TSA baths have superior corrosion resistance when com-
pared with their counterparts produced from sulfuric acid baths
[12,23]. It has been suggested that residual tartaric acid left inside
the pores after the anodizing process [24] may form chelates com-
plexes with Cu(II) cations present in the anodic film reducing the
heterogeneities of this latter [23]. Boisier et al. [12] have con-
cluded that sealed TSA anodized layers produced on AA2024-T3
substrate presents superior corrosion resistance than those pro-
duced in dilute sulfuric acid due to the higher compactness of
the porous layer and higher resistance of the barrier layer. On the
other hand, Garcia-Rubio et al. [5] have shown that hydrothermally
sealed TSA clad Al 2024-T3 alloy has similar corrosion resistance to
that exhibited by similar samples sealed in hot dichromate solution.
In this study, a post-treatment process based on the use of a
hybrid sol–gel film applied on clad AA 2024-T3 anodized in a TSA
bath is proposed. These films are reported to be environmentally
friendly alternatives to replace chromate conversion coatings. Their
synthesis is based on the sol–gel process which consists in hydrol-
ysis and condensation of metal or silicon-alkoxides precursors,
forming thin, dense and chemically inert films on substrates. In the
case of hybrid organic–inorganic sol–gel coatings, precursors con-
taining non-hydrolysable groups are used to incorporate an organic
part in the coating. This organic contribution provides flexibility,
reduces defects and improves compatibility with polymer coatings
while the inorganic constituent provides superior adhesion to the
metal surface and improves scratch resistance [25–30].
This work focuses on the comparison of the corrosion resistance
of TSA anodized clad AA2024-T3 protected with this new system
with that exhibited by samples sealed in boiling water. The cladding
allows avoiding in this first approach the interference of the cop-
per intermetallics on the anodic layer morphology and properties
[31]. The morphology of the anodic films and their thicknesses were
evaluated by scanning electron microscopy (SEM), field emission
scanning electron microscopy (FE-SEM) and glow discharge optical
emission spectrometry (GDOES). In addition, corrosion proper-
ties of the barrier, porous and sealed layers were determined by
electrochemical impedance spectroscopy (EIS), which is a quick,
non-destructive method providing reliable results about corrosion
protection behavior. EIS data were interpreted on the basis of elec-
trical equivalent circuits consisting of a combination of resistances
and capacitances associated in series or in parallel providing the
same electrical response as the studied electrochemical interface
[7,10,32–35].
The novelty of the proposed system relies on the fact that,
to the best of the authors’ knowledge, no study is avail-
able in the literature where cladded or uncladded anodized Al
alloys have been protected with hybrid films. In addition the
compatibility of the organic precursor used in the present study (3-
glycidyloxypropyl)trimethoxysilane (GPTMS)) with epoxy-based
painting systems may constitute a major achievement for the
aerospace industry as, at present, paintings are only applied to
non-sealed anodized layers, which, recognizably, present inferior
corrosion resistance than the sealed ones [5,12].
2. Experimental
The clad aluminum alloy AA2024-T3 was supplied by SONACA
S.A (Gosselies, Belgium). The nominal composition of clad layer is
0.7 wt.% Si + Fe, 0.1 wt.% Cu, 0.05 wt.% Mn, 0.05 wt.% Mg, 0.1 wt.%
Zn, 0.03 wt.% Ti and 0.03 wt.% others. The specimens of size
5 cm × 10 cm × 0.126 cm were degreased by sonication in acetone
for 10 min and immersed in a commercial alkaline degreasing
bath (Turco 4215 NCLT) at 50 ◦ C for 10 min. Before anodizing, the
samples were dipped in an alkaline etching bath (NaOH solution,
40 g L−1 ) at 40 ◦ C for 30 s and in a chromate-free commercial acid
dismutting bath (Turco Smuttgo) at room temperature for 15 s.
Between each step, the specimens were rinsed in deionized water.
The anodizing process was performed in a tartaric-sulfuric
acid bath (TSA). It was carried out in a solution of 40 g L−1
H2 SO4 + 80 g L−1 C4 H6 O6 at a constant voltage of 14 V (current
density between 0.32 and 0.35 A/dm2 ) for 20 min at 37 ◦ C. After
anodizing, the samples were rinsed with deionized water and then
either sealed in boiling deionized water for 25 min or protected
with a hybrid organic–inorganic coating applied by the sol–gel
route for 2 min.
Sol–gel films were prepared as follows: tetraethoxysilane
(TEOS) (20 %v/v) and (3-glycidyloxypropyl)trimethoxysilane
(GPTMS) (10 %v/v) were added in a mixture of ethanol (10 %v/v)
and distilled water (58 %v/v). The pH was adjusted by acetic acid in
the range of 2.3–2.5. The solution was stirred at room temperature
for 2 h in order to allow hydrolysis of the alkoxy groups. The
anodized samples were immersed in the hydrolyzed solution and
maintained for 2 min by a dip-coating process. The withdrawal rate
was fixed at 100 mm/min. The samples were then cured at 150 ◦ C
for 1 h in an oven. All the reagents were purchased at Aldrich and
used as received without further purification.
The morphological characterization of the samples was deter-
mined using a Philips XL-20 and an Oxford WDX 600 scanning
electron microscope (SEM) coupled to an energy dispersive X-ray
spectrometer analyzer (EDX). The FE-SEM (field emission scan-
ning electron microscopy) surface characterization was carried out
using a FEI Inspect F50. Composition profiles were recorded in
depth by GDOES using a Horiba Jobin Yvon profiler instrument
operated at Ar pressure of 650 Pa and power of 25 W. The atomic
percentage accuracy is around 50 ppm for the element signals such
as O, H, S, P, N and higher for the others.
The corrosion protection provided by the different treatments
was evaluated by means of electrochemical impedance spec-
troscopy (EIS). Electrochemical tests were performed using a
Princeton Applied Research Parstat 2273 (Ametek) potentiostat-
frequency analyzer controlled using Power Suite software. A
classical three electrodes arrangement was used. An Ag/AgCl
(+0.207 V vs. SHE) electrode and a platinum plate were used as ref-
erence and counter electrode, respectively. EIS measurements were
performed using signal amplitude of 20 mV (rms) and the frequency
was ranged from 105 to 10−2 Hz. The contact immersed area was
7.0 cm2 . The impedance measurements were performed after dif-
ferent immersion times in a 0.5 M NaCl naturally aerated solution
at room temperature. Accelerated corrosion tests were carried out
in a salt spray chamber Q-FOG Cyclic Corrosion tests (Labomat).
The samples were exposed for 1008 h (42 days) using 5 wt.% NaCl
solution (6.5 < pH < 7.2) with a spray flow rate of 40 mL h−1 , accord-
ing to standard ASTM B117-07a [36]. During the test the chamber
was kept at 35 ± 1 ◦ C. The samples were periodically removed from
the chamber for visual evaluation of the extent of corrosion. The
coating efficiency was visually assessed by comparing the size of
the corroded area before and after the test.
3. Results and discussion
3.1. Morphological characterization
Fig. 1 presents the FE-SEM micrographs of the surface of anodic
layers unsealed, hydrothermally sealed (after 25 min of sealing in
boiling water) and coated with the hybrid sol–gel. As shown in
Fig. 1(a), the porous structure of the anodic layer is clearly observ-
able before sealing. The pore distribution is regular with an average
 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79 71

Fig. 1. FE-SEM micrographs for AA2024-T3 clad anodized by TSA and (a) unsealed, (b) sealed with water and (c) protected with the hybrid sol–gel.

diameter close to 8 nm. The hydrothermal sealing strongly modifies aluminum content due to the roughness of the alloy/film interface
the surface (Fig. 1(b)). The initial porous structure is not observable and a region showing a constant aluminum concentration relative
anymore and a layer of “petal-shaped” crystals, so-called smudge, to the bulk alloy. Sulfur resulting from sulfuric acid and oxygen
covers the entire surface. Initial dissolution of the pore walls is fol- species are only detected in the anodic layer. These S and O
lowed by precipitation of the aluminum hydroxide which plugs the profiles confirm that the thickness of the anodized layer is close
upper part of the pores [10,37–40]. This result is in agreement with to 3 ␮m. The carbon content is very low (lower than 0.2 atomic
Boisier et al. [12] who observed that these “petal-shaped” crys- %) in the anodic layer meaning that tartaric acid has only little
tals grow when the sealing period is increased forming a dense effect on the layer composition. This result confirms that this
layer on the surface. The deposition of the hybrid sol–gel coating acid, which is a weak acid (only partially dissociated), is not very
tends to smooth the surface of the anodized sample (Fig. 1(c)). The aggressive toward the metal and its oxide and cannot contribute
hybrid film seems to cover the porous structure and form a thin
and uniform coating on the surface. The homogeneity of the sol–gel
coating can be related to the presence of a hydroxyl-rich oxide layer
on the clad AA2024-T3 anodized surface which promotes strong
interactions between the substrate and the silanol groups of the
hydrolyzed precursors [27]. The SEM micrograph (Fig. 2) of cross
section of unsealed anodic film formed in TSA is used directly to
determine the thickness of the anodic layer which is approximately
3 ␮m. For the used experimental conditions, this value is in good
agreement with the literature [5,12].
GDOES combines the sputtering of the sample with atomic
emission, enabling the depth profiles of different elements present
in the anodic layer to be displayed. Fig. 3 presents the GDOES pro-
files obtained for the different samples: unsealed, sealed by boiling
water and protected with the hybrid coating anodized layers. Three
different regions can be differentiated from the external surface
considering the Al depth profile of the unsealed anodized speci-
men (Fig. 3(a)): the porous anodic film showing approximately a Fig. 2. SEM observation of cross section of unsealed anodic film formed in TSA
constant aluminum content, a quite broad region with increasing solution.
72 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79

100
(a)
90

80
O
70
C
composition (at %)

60 Al S

50 Al

40
O
30

20

10
S
0
0 2 4 6 8 10
Fig. 4. Comparison of the glow discharge optical emission spectrometry profiles of
depth/µm C, O, Si and S for TSA anodized samples hydrothermally sealed and protected with
100 the hybrid sol–gel.
(b)
90
to the formation of the anodic film at the applied voltage (14 V).
80 The sulfuric acid thus is the main reservoir of mobile protons
Al involved in the growth of the oxide layer. The tartaric acid only
composition (at %)

70 enables to limit the dissolution rate occurring at the base during

O
pore formation. These results are in accordance with the findings
60 C of Curioni et al. [24]. These authors suggested that tartaric acid
50 S derived species are not significantly incorporated in the oxide film
during anodizing in TSA bath and showed that the anodic layers
40
Al are not morphologically different from those produced in sulfuric
O acid baths. However, they have demonstrated that residual tartaric
30
acid remains in the pore solution, which would have an important
20 role during posterior hydrothermal sealing treatment improving
the corrosion behavior of the sample.
10
S After sealing with boiling water (Fig. 3(b)), four regions can be
differentiated in the element profiles. The anodic layer is com-
0 posed of two distinguishable regions. An upper layer of about 1 ␮m
0 2 4 6 8 10
richer in oxygen appears and can be attributed to the precipita-
depth/µm
tion of aluminum hydroxide into the pores. According to Wefers
100
[37], the chemical nature of these precipitates seems to be close
(c) to pseudoboehmite or boehmite (AlOOH). Despite the fact that a
90
duration of 25 min was sufficient to meet the quality standards of
80 Si O
traditional control tests, this sealing time seems to be insufficient
Al to seal the anodic layer on its whole thickness, which is consistent
70 C
composition (at %)

with findings of other authors [12]. More than 1 ␮m of the layer is

60 S not modified in composition by the sealing process.
Al For the specimen protected by the sol–gel hybrid coating, the
50 Si Si profile can be used to identify the sol–gel layer. As observed in
Fig. 3(c), four regions can also be distinguished. At the top surface,
40 only Si, O and C atoms can be detected and attributed to the depo-
sition of uniform and thin layer of sol–gel. This result confirms the
30
O (c)
observation made by FE-SEM. The transition between the anodic
20 layer and the sol–gel film is sharp and the coating thickness can be
evaluated at 400 nm by this technique. As expected, the anodic layer
10
S is rich in oxygen and in aluminum. The oxygen atomic percentage
is slightly higher in the external anodic layer. In order to identify
0
0 C 2 4 6 8 10
the presence of sol–gel in the anodic porous layer, the GDOES pro-
depth/µm files of the anodized samples sealed with water and coated with
the hybrid sol–gel were compared using a y-axis of 5 atomic % in
Fig. 3. Glow discharge optical emission spectrometry profiles of TSA anodized sam- full scale (Fig. 4). These data evidenced that the Si and C contents
ples (a) unsealed, (b) hydrothermally sealed and (c) protected with the hybrid are not negligible in the anodic layer confirming the presence of
sol–gel. a small amount of hybrid sol–gel coating inside the pores through
the entire thickness. The Si, C and O contents strongly decrease in
the broad oxide/aluminum interface and become negligible in the
bulk matrix.
 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79
Fig. 5. Bode diagrams in modulus and in phase for clad AA2024-T3 anodized with
TSA and unsealed versus immersion time in 0.5 M NaCl.
GDOES depth profiles and the FE-SEM images are in agreement
and show that the hybrid sol–gel coating can penetrate through the
anodized layer and block the pores entrance.
3.2. Electrochemical characterization
3.2.1. EIS on unsealed anodized aluminum
The EIS measurements (Fig. 5) for unsealed TSA anodized Alclad
2024-T3 were carried out for different immersion times in 0.5 M
NaCl solution until 1008 h of immersion. Two time constants can
be observed in the Bode diagrams for immersion times higher
than 48 h. The time constant which slightly appears at high fre-
quencies is related to the unsealed porous layer and the one at
lower frequency range to the barrier layer. The Bode diagrams were
fitted with two time constants in series till 168 h of immersion
(Fig. 6(a)) [10,41]. The physical model associated to this inter-
face takes into account that when an unsealed anodized layer is
exposed to an aqueous electrolyte the pore is initially filled by the
solution and that, afterwards, a progressive autosealing process
occurs throughout the pore depth due to dissolution of anhydrous
alumina from the pore walls and its precipitation as hydrated
alumina resulting in pore widening and progressive pore blocking
[40].
73
Fig. 6. Equivalent circuits used to fit the EIS behavior of the unsealed anodic films
(a) up to 168 h of immersion and (b) from 356 h till 1008 h of immersion in 0.5 M
NaCl solution.
In order to consider the non-homogeneous structure of the
layers, it is preferable to simulate the capacitive behaviors by using
constant phase elements (CPE) rather than pure capacitances.
The following equation is proposed in the literature [42] for the
impedance of a constant phase element: ZCPE = 1/Y0 (iω)−n . The
parameter n is the frequency dispersion factor and varies from 0
to 1. When n = 1 the CPE can be considered as a capacitor, whereas
n = 0 represents a resistor. The porous layer is characterized by the
electrolyte resistance through the pores Rp and its associated CPEp .
The evolution of these parameters is associated to the changes in
the EIS response due to the progressive precipitation of hydrated
alumina inside the pores during the partial sealing process that
occurs with unsealed anodized layers when exposed to aggressive
electrolytes [5,19,30]. Up to 168 h of test it is considered that this
auto-sealing process is incipient (Fig. 6(a)) and does not contribute
significantly to increase the impedance of the pores. A resistance
Rb and a capacitance CPEb describe the barrier layer which is the
main responsible for the corrosion resistance of the system [7]. For
the barrier layer, the CPE is practically a pure capacitance with a
n value superior to 0.96, indicating that this part of the protective
system is fairly homogeneous and free of defects, therefore we
have used the CPEb value to estimate the thickness of the barrier
layer with the expression (1) [12]:
ε0 εr S
Cb = (1)
eb
(ε0 = 8.854 × 10−14 F cm−1 , εr = 10 [10], S = 7 cm2 ). The thickness
determined after 1 day of immersion has an average value of
19 nm. This value is in good agreement with the literature [43]. For
longer exposure times (superior to 168 h), one parallel branch was
added to describe the EIS response of the pore walls (Fig. 6(b)).
This component can be omitted at the beginning of immersion
because the impedance associated to the pore walls is extremely
high and the impedance of the pores filled with precipitated
hydrated alumina is low, therefore this time constant is out of the
investigated frequency range. After immersion time higher than
168 h, the capacitive response of the pore walls can no longer be
neglected, however the resistance associated with the pore walls is
still very high and do not appear in the CE scheme [5,12] (Fig. 6(b)).
A resistance R related to the electrolyte in the pores and the defects
of an intermediate layer appears in parallel with this capacitance
[10] and in series with CPEp //Rp . This R is very low, between 200
and 300 cm2 , indicating it does not hinder penetration of aggres-
sive species. The capacitive response of the pore walls (Cpw ) is
74 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79
Fig. 7. RP and Rb values versus immersion time in 0.5 M NaCl for unsealed anodic
film formed in TSA solution.
represented by a pure capacitor. Its value almost does not change
with immersion time, except after 1008 h of test, when the dete-
rioration of the anodized layer was evident. The value of CPEb
remains almost constant during the whole test, indicating that it
is quite stable.
Fig. 7 presents the fitting data values of Rp and Rb determined by
using the models of Fig. 6(a) up to 168 h of immersion and Fig. 6(b)
between 168 and 1008 h of immersion. As shown on Fig. 7(a), Rp is
very low just after anodizing and increases with immersion time.
This increase can be associated to the sealing of the layer by forma-
tion of precipitates occurring with long immersion times in water
at ambient temperature [19]. It is significant that during the test
the CPEp value (in the order of 10 ␮F. cm−2 s(n−1) ) slowly decreased
with immersion time. This is coherent with the fact that the per-
mittivity of the hydrated alumina that precipitates inside the pores
is lower than that of free water [30]. On the other hand the “n”
parameter remained close to 0.5, which can be associated with the
porosity of this precipitated layer [12]. Rb also seems to increase
with immersion time (Fig. 7(b)) suggesting the oxide reinforcement
by the formation of corrosion products in the base of the pores. It
is worth noting that the surface is highly degraded with numerous
pits at the end of the test (1008 h), however the extremely high low
frequency impedance value (superior to 10 M cm2 ) obtained for
this test condition indicates that these pits are only superficial and
do not pierce the anodizing layer reaching the substrate.
Fig. 8. Bode diagrams in modulus and in phase for AA2024-T3 clad anodized with
TSA and hydrothermally sealed versus immersion time in 0.5 M NaCl.
3.2.2. EIS on sealed and hybrid protected anodized Alclad 2024-T3
Figs. 8 and 9 show Bode impedance plots versus immersion time
for the anodized Alclad samples sealed by boiling water or coated
with the hybrid sol–gel film, respectively.
In comparison with unsealed anodized samples (Fig. 5), EIS
spectra of water sealed and hybrid post-treated anodized samples
(Figs. 8 and 9) exhibit two times constants well distinguishable
from the first immersion times. The time constant in the low-
frequency part of the diagram is attributed to the barrier layer
response and indicates the effective corrosion resistance of the sys-
tem [5,7,14]. The physical transformations occurring in the porous
layer are reflected in the changes taking place in the time constants
in the high and medium frequency ranges of the diagrams [5] what-
ever the post-treatment employed.
Only one equivalent circuit model was needed to fit the whole
set of EIS data for the post-treated samples. It is presented in Fig. 10
associated with the physical models for both treatments. These
latter were conceived according to the results obtained with the
GDOES technique, which indicated a partial sealing of the porous
layers for the hot water treatment and a penetration of the coating
into the pores for the sample protected with the hybrid. Therefore,
for the hybrid coated sample the resistive and CPE elements char-
acterizing the EIS response inside the pores of the anodized layer
 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79 75

Fig. 9. Bode diagrams in modulus and in phase for AA2024-T3 clad anodized with
TSA and protected with the hybrid sol–gel coating versus immersion time in 0.5 M
NaCl.

were denominated RHL and CPEHL to differentiate from the usual

denomination for these elements in water sealed anodized layer,
Rp and CPEP . This electrical equivalent circuit is in agreement with
the literature for sealed anodized aluminum [10,14,34,35].
For the hydrothermally sealed sample it is important to note
that the n value associated to the CPE response inside the pores
(CPEP ) was maintained fixed at 0.5 to fit with low error value. This
relatively low value is associated with the complex nature of the
aluminum hydroxide within the pores [14,35] and can be related
with the porous nature of this product [14]. For these samples, the
properties of the porous layer seem to be very stable with time since Fig. 10. Equivalent circuits used to model the EIS behavior of the anodized layers
no significant modification of the time constant at high frequen- (a) hydrothermally sealed and (b) protected with the hybrid sol–gel coating.
cies is observed. In the opposite, as shown in the phase diagram of
Fig. 8, the barrier layer loses its capacitive behavior with time and not observable in the analyzed frequency range. The time con-
the phase angle decreases significantly at low frequencies with a stant in the range of medium frequencies attributed to the porous
behavior becoming more resistive. This is accompanied by a slight layer filled by the sol–gel (CPEHL //RHL in Fig. 10(b)) is observ-
diminution in the low frequency impedance modulus, indicating able on a large frequency range at short immersion periods but
sample deterioration [7]. is subjected to changes with time, being progressively split into
For the samples protected with the hybrid sol–gel (Fig. 9), the two easily differentiated processes, probably due to a loss of the
time constant at higher frequencies is developed on a larger fre- barrier properties of the sol–gel layer at the top surface. This
quency range compared to the hydrothermally sealed samples. loss of barrier properties also induces a loss of the modulus at
The time constant at low frequencies is shifted toward lower fre- low frequency, and a slight displacement of the low frequency
quencies than for hydrothermally sealed one and a large part is phase angle to higher frequencies, indicating a decrease of the
76 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79
Fig. 11. (a) Rb , (b) CPEb , (c) RP and RHL and (d) CPEP and CPEHL values for hydrothermally sealed and hybrid sol–gel coated anodic films formed in TSA versus exposure time
in 0.5 M NaCl solution.
protective properties. This time constant becomes again stable
between 168 and 672 h most likely due to the blocking of the pore
s entrance by the hybrid sol–gel. With time, a third time constant
appears at high frequencies relative to the capacitive behavior of
the pore walls.
For the sample protected with the hybrid layer, the physi-
cal model of the interface presented in Fig. 10(b) shows that the
changes occurring in CPEHL //RHL are related to the properties of the
sol–gel layer deposited on the pores mouths and inside the pores.
On the other hand, the capacitance of the sol–gel film deposited on
top of the pore walls can be neglected because the thickness of the
uniform sol–gel film is at least one order of magnitude lower than
the pore wall thickness, as demonstrated by GDOES technique. The
lower capacitance of this latter has a dominant effect as placed in
series. For these particular samples, the resistances of the barrier
layer (Rb ) cannot be accurately estimated by the EIS fitting due to
the behavior mainly capacitive at low frequency. The characteristic
frequencies of this particular time constant is well below the lowest
frequency employed in the study [5,10,30], which is evident from
the fact that in the low frequency limit the phase angle diagrams
are in their ascending region and show no inflection point. On the
contrary, Rs is usually a few ohms and can be only observed at very
high frequencies (above 105 Hz).
Fig. 11 summarizes Rb , CPEb , Rp /RHL and CPEp /CPEHL values
obtained by fitting for the anodized samples hydrothermally sealed
or protected with the hybrid sol–gel coating. For the samples
hydrothermally sealed, the Rb values versus exposure time in
0.5 M NaCl are high (Fig. 11(a)) and remain practically constant for
the first 168 h of immersion. After this time, a sharp decrease is
observed indicating that the barrier layer is attacked due to the
relative low protection afforded by the sealed porous layer. This is
consistent with the fact that the porous layer is not homogeneously
sealed along the entire length of the pores as shown by GDOES.
Therefore, it is likely that after aggressive species have penetrated
the outer sealed region they can reach the barrier layer damaging
it.
As observed in Fig. 11(b), whatever the sealing process, the
CPEb values are very close meaning that this parameter is only
depending on the anodizing process and is independent of the
post-treatment step. As this CPE is close to a pure capacitance (nb
between 0.96 and 1), and so inversely proportional to the layer
thickness (about 20 nm), the barrier thickness is constant whatever
the investigated sealing mode and is not affected during the aging
by immersion in aggressive solution. The RHL of the sample pro-
tected by the hybrid sol–gel coating (107  cm2 ) is particularly high
compared to the pore resistance (RP ) obtained after water sealing
(105  cm2 ) as shown in Fig. 11(c). Nevertheless, this latter remains
stable with time whereas a slow decrease of RHL for the samples
protected with the sol–gel is observed during the first hours of
immersion confirming the loss of the film barrier properties. RHL
 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79 77

Fig. 12. Microscopic images of TSA anodized samples obtained after (a) 168 h, (b) 336 h, (c) 504 h and (d) 672 h of exposure in salt spray test.

value reaches around 3 × 106  cm2 after 168 h of immersion. This
value becomes quite constant for higher immersion times. The
data presented in this Figure indicate that the treatment with the
hybrid sol–gel constitutes a more effective barrier against aggres-
sive species penetration through the pores of the anodized layer
than the hydrothermal sealing. Finally, the values of CPEP and CPEHL
are difficult to compare in absolute values because their behaviors
are not purely capacitive (Fig. 11(d)). However, the values are one
order of magnitude lower for the samples protected with hybrid
sol–gel coating. This difference can be partially explained by the
higher global thickness due to the presence of the sol–gel coating
and a small modification of the dielectric constant of the layer.
78 V.R. Capelossi et al. / Electrochimica Acta 124 (2014) 69–79
The electrochemical results showed that the protection of the
clad and anodized AA 2024-T3 with thin hybrid films improved
the performance against corrosion due to the formation of a homo-
geneous surface film which hinders the electrolyte penetration in
the pores and fills the porous layer as confirmed by morphological
surface characterization.
3.3. Salt spray test
To correlate the trends deduced from EIS measurements with
the corrosion resistance properties, salt spray test was carried
out according the ASTM B117-07 [36]. The samples were visually
observed after different exposure times: 24 h, 72 h, 168 h, 336 h,
504 h and finally 1008 h. The optical microscopy images are pre-
sented in Fig. 12 after 168, 336, 504 and 672 h of exposure. As
observed, the unsealed samples were quickly degraded during
exposure. Some pits can be observed after 168 h. For longer expo-
sure times, pits increase in number and in size and cover the
whole surface. The results showed a significant enhancement of
salt spray resistance after hydrothermally sealing or hybrid sol–gel
treatment. The samples sealed by boiling water present a good cor-
rosion resistance with only apparition of one pit on the analyzed
surface. The number of pits remains quite low with time. The sam-
ples protected with the hybrid sol–gel coating present a different
behavior. They are less sensitive to pitting corrosion. No deep pits
are observed even at the end of the test but the appearance of the
samples is nevertheless modified with exposure. A kind of blister-
ing in surface seems to appear but mainly present in surface. At
the end of the test, the surface seems to have been submitted to a
peeling phenomenon. The uniform and thin sol–gel initially cover-
ing the top surface is disappeared but the small amount of sol–gel
present inside the porous layer seems to be able to avoid the pitting
of the aluminum alloy.
4. Conclusions
Anodic films generated in tartaric-sulfuric bath on clad AA2024
alloy were characterized morphologically by FE-SEM and GDOES
profiles and electrochemically by EIS. The GDOES profiles indicate
that water sealing of 25 min is not sufficient to seal the porous layer
on the whole length even if this duration is enough to meet the
industrial quality standards and evidence the penetration of the
hybrid coating in the pores of the anodized layer. The comparison of
hydrothermally sealing and treatment by sol–gel coating highlights
the promising results obtained by this new way. The sol–gel coating
deposition allows a uniform coverage of the whole surface, plug-
ging the entrance of the porous layer and filling at least partially
the pores. The corrosion behavior evaluated by EIS measurements
and EC fitting revealed that the presence of the hybrid layer inside
the pores of the anodized layer protected with the sol–gel treat-
ment increases the resistive properties of the pores compared to
the hydrothermal sealing, delaying the access of aggressive species
to the barrier layer. These results are confirmed by salt spray since
the samples sealed by sol–gel are less sensitive to pitting corrosion.
This behavior could be explained by the sol–gel presence inside
the porous layer. For long exposure time (>332 h), a blistering phe-
nomenon is however observed in surface due to the delamination
of upper sol–gel layer.
Acknowledgements
R.P.B. Hernández and V.R. Capelossi are grateful to CNPq and
CAPES for Post-doctoral grants. This project was financially sup-
ported by CAPES/WBI (project 012/10). Isaline Recloux wishes
to thank the FRIA (Fonds pour la Formation à la Recherche
dans L’industrie et l’Agriculture) for funding. This study was
also done in the framework of the Opti2mat “Program Excel-
lence” financed by the Region Wallonne (Belgium). The authors
acknowledge the Brazilian Nanotechnology National Laboratory
(LNNano) for the FE-SEM images and Alex Lanzutti of Uni-
versity of Udine (Italy) for GDOES profiles. The authors also
acknowledge Francesca D’Emidio for the support in salt spray
test.
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