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ECS Transactions, 43 (1) 57-64 (2012)

10.1149/1.4704940 The Electrochemical Society

Corrosion Protection of Aluminum Alloys by Methoxy-Silanes(SAM)/Polyaniline


Double Films
Daiane P. B. Silvaa,b, Rodrigo S. Nevesc and Artur J. Motheo a
a

Instituto de Qumica de So Carlos, USP, So Carlos, SP, 13566-590, Brazil


b
Departamento de Qumica, UFSCar, So Carlos, SP, 13565-905, Brazil
c
Diviso de Metrologia de Materiais, Inmetro, Duque de Caxias, RJ,25250-020, Brazil

The development of alternative methods for aluminum alloys


corrosion protection is as an important object of study in
electrochemistry and materials engineering, due to economic and
environmental reasons. In this context, this work presents a study of
the electrochemical behavior of aluminum alloys (AA1050 and
AA2024) coated with self-assembled monolayers (octadecyl- and
propyl-trimethox-silane)-polyaniline double films by using
potentiodynamic polarization curves and electrochemical impedance
spectroscopy. The results have showed that both the double films
present protective behavior. However, the double film with
octadecyl-trimethoxy-silane is more stable and effective when the
samples are exposed to the corroding media for a longer period.

Introduction
The protection of aluminum alloys against corrosion is extensively studied in the fields of
electrochemistry and materials science, because these alloys are used in diverse industrial
areas and undergo processes of localized corrosion. Aluminum is naturally covered by an
oxide layer which is stable in the pH range between 4 and 9 and, under these conditions,
this layer acts as a natural protection against corrosion (1, 2). In the case of alloys, small
amounts of alloying elements are combined with the aluminum matrix in order to improve
mechanical properties, however, these same elements make the material susceptible to
corrosion.
Several approaches are used to curb corrosion of aluminum. One common and versatile
one is the application of coatings onto the material, which avoid the access of corroding
species to the surface. The materials often used for coatings, as chromium, for example,
have high toxicity and represent a serious risk to the environment and, as a result, there are
several studies related to the development of environmentally friendly coatings. Two
interesting groups of materials whose can be used to obtain this kind of coating are the
conducting polymers (3), as polyaniline (PAni) and polypyrrole, and the self-assembled
monolayers (SAM) (4), mainly those made of organosilanes and diphosphonic acids.
PAni was the first conducting polymer used for corrosion protection. Not only does it
act as barrier to the corroding species, but it also provides anodic protection, due to its
multiple levels of oxidation. The SAMs also acts as a barrier to the corroding species and,
furthermore, they can be used as a prime to promote adhesion of a second coating, which

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ECS Transactions, 43 (1) 57-64 (2012)

might be a conducting polymer. Therefore, the combination of both coatings has shown
great potential for aluminum corrosion protection (5, 6).
In this context, this work present a study of the use of SAMs and PAni films for
corrosion protection of aluminum alloys. The alloys chosen for the study were the AA2024,
often used by the aircraft and military industries, and the AA1050, for comparison. The
SAMs used as coatings were the octadecyl-trimethoxy- and propyl-trimethoxy-silane
(ODTMS and PTMS, respectively), which are suitable choices due to the simplicity of the
SAM deposition method. For the polymer coating deposition, a saturated solution of
undoped PAni in N-methyl-pyrrolidone (NMP) was used to paint the samples previously
coated with ODTMS and PTMS.
The corrosion protection performance of the SAM-PAni coatings, for each one of the
alloys, was studied by using potentiodynamic polarization curves and electrochemical
impedance spectroscopy (EIS). Additionally, the surfaces were analyzed, before and after
the corrosion tests, by using scanning electron microscopy (SEM).

Experimental Procedure
Pre-treatment of the Samples
Aluminum alloys samples (geometric area = 1.13 cm2) were polished using emery paper
from P100 to P1200 grades in order to obtain a surface with homogeneous distribution of
scratches. During this process the samples were constantly rinsed with type 1 water. The
polished samples were immersed during one hour in glacial acetic acid (Mallinckrodt PA)
aqueous solution (pH = 3) under sonication. After this, the samples were dried in air. This
procedure results in a surface with finishing equivalent to those of aluminum used for
industrial applications. The samples submitted to this process were called bare samples.
Deposition of the SAMs
The SAMs depositions were carried out by immersion of the bare samples for 10 minutes
into a solution containing 0.75 % in volume of the organosilanes (PTMS or ODTMS, both
from Fluka and 90% pure) in a 1:9 water (type 1): anhydrous ethanol (Aldrich PA)
mixture. The pH of this solution was adjusted around 4 by adding glacial acetic acid. After
this procedure the solution was stirred for 10 minutes to ensure total hydrolysis of the SAM
precursor. The bare samples were immersed for 10 minutes in this solution and dried with
nitrogen. This procedure results in aluminum surfaces covered by stable and homogeneous
SAMs (7).
Deposition of PAni Films
After SAM deposition, the samples were coated with PAni film in order to obtain the
double films. For this intent, a saturated PAni solution was prepared by adding 7% in mass
of undoped PAni (chemically synthesized) into N-methyl-pyrrolidone (NMP) and
submitting this solution to a sonic bath for 15 minutes. The samples were painted with this
solution and dried at 50 C, under vacuum, for 3 hours. This process was repeated 2 more
times in order to result in a homogeneous polymeric film.

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ECS Transactions, 43 (1) 57-64 (2012)

Electrochemical Experiments and Characterization of the Samples


The electrochemical system used in this study was composed of a single compartment
electrochemical cell, a saturated calomel electrode (SCE), used as reference electrode, a
platinum sheet (geometric area = 2.5cm2), used as counter electrode and the prepared
aluminum samples as working electrodes. NaCl 0.6 mol dm-3aqueous solution was used as
working solution.
Polarization curves were registered into a region of potential of 1 V around the open
circuit potential (OCP) and with a sweep rate of 0.5 mV s-1. All the polarization curves
were registered by using an EG&PAR model 273A potentiostat. EIS experiments were
performed in the OCP, for different times of immersion of samples in the working solution,
in order to verify the coatings stability. The frequency range was from 10 mHz to 100 kHz
(10 points per decade) and the signal amplitude was 10 mV rms. All the EIS experiments
were performed by using an AUTOLAB Eco Chemie, model PGSTAT 30, potentiostat.
Additionally, before and after the corrosion tests, the samples were analyzed by
scanning electron microscopy (SEM) in a Zeiss Leica DSM 960 microscope operating at
15 20 kV.

Results and Discussion


Potentiodynamic Polarization Curves
The polarization curves, which can be observed in figure 1a, show that the bare samples
of both alloys exhibit values of corrosion potential (Ecorr) and pitting potential (Epit) close to
each other. This is evidence that pitting corrosion occurs almost simultaneously to uniform
corrosion when the samples are exposed to solutions containing aggressive species, like Cl-.
Polarization curves were also registered for the samples coated with SAMs, PAni and the
SAM-PAni double films. The Ecorr calculated from these polarization curves are compared
with the results obtained for the bare samples in figure 1b.
From this comparison of results, it is possible to observe positive shifts in Ecorr values
for all the coated samples, indicating that the coatings provide anodic protection. The
results obtained for the SAM coated samples show that ODTMS was more effective to
protect both alloys against corrosion. This is related to the larger number of carbon atoms
present in the ODTMS aliphatic chain (18 atoms) when compared to PTMS (3 atoms), that
leads to the formation of coatings more homogeneous and with fewer defects (8). Besides,
the ODTMS coating acts as an extra barrier to corrosion.
When the different alloys are coated only with PAni, Ecorr values are also shifted to
more positive values. The comparison between Ecorr displacements related to the ODTMS
and PAni coatings shows that in the case of the AA2024 alloy, the PAni coating results in a
larger displacement.

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ECS Transactions, 43 (1) 57-64 (2012)

b)

-0,25
-0,50

600
AA2024

500

Ecorr / mV

E / V vs. SCE

a)

-0,75
-1,00

AA1050

-1,25

400
300
200
100

-8

-6
log (i

-4

-2

/ A cm

-2

AA1050

AA2024

Figure 1. (a) Polarization curves for the AA1050 and AA2024 alloys in 0.6 mol dm-3NaCl
aqueous solution (0.5 mV s-1, T = 25 C). (b) Decrease of Ecorr (%) for the different coatings
compared to the bare samples: ( )PTMS, ( )ODTMS, ( )PAni, ( )PTMS + PAni
and ( )ODTMS + PAni.
This behavior is possible related to the larger amount of copper in the AA2024 alloy
(between 3.8 and 4.9%) when compared to AA1050, which is copper free. As mentioned
before, besides acting as a physical barrier to corroding species, PAni also can absorb
charges from the solution through changes in its oxidation states, which seems to improve
the coating protective behavior for alloys with higher amounts of metals with reduction
potential higher than that of aluminum, as is the case of copper.
When the alloys are covered by the SAM-PAni double films, it is perfectly clear that
the combination of properties of the different films leads to a synergistic effect on the
coatings anodic protection in the case of AA1050 and AA2024 alloys.
The polarization curves show the changes in the protective behavior of the different
coatings when the SAMs and PAni films are deposited separately onto the samples and
when SAM-PAni double films are used. However, no information concerning to changes in
other coatings characteristics are assessed, as the film capacitance and the coating stability.
To this aim, the different coatings were also studied by using EIS.
Electrochemical Impedance Spectroscopy
The Bode plots obtained for AA1050 samples coated with different films, for 1 and 60
hours immersed in the corroding medium can be observed in fig. 2. The plots in figs 2a and
2b, for 1 hour of immersion, show that the PTMS coating does not originate any
considerable change in the alloy impedance behavior. On the other hand, the ODTMS
coating rose substantially the impedance of the system (fig 2a). This behavior is related to
the size of the ODTMS molecule, as discussed before. Additionally, the plots related to
ODTMS show one predominant capacitive domain at the high frequency region, clearly
related to the SAM capacitive behavior. The results obtained for the PAni coating, on the
other hand, show two distinct capacitive domains related to the corrosion protection
mechanism based on the barrier effect and on changes in the PAni oxidation level.

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ECS Transactions, 43 (1) 57-64 (2012)

a)

6
5
log (|Z| / )

log (|Z| / )

5
4
3

4
3

1
-2 -1 0 1 2 3 4 5
log (f / Hz)

-2 -1 0 1 2 3 4 5
log (f / Hz)
b)

d)

80

80

70

70

60

60

50

50

c)

40

40

30

30

20

20

10

10
-2 -1 0 1 2 3 4 5
log (f / Hz)

-2 -1 0 1 2 3 4 5
log (f / Hz)

Figure 2. Bode plots for the AA1050 alloy with different coatings in 0.6 mol dm-3NaCl
aqueous solution. a)log |Z| - 1h immersed. b) phase angle 1h immersed. c) log |Z| - 60h
immersed. d) phase angle 60 h immersed: ()bare sample; ({)PTMS, (U)ODTMS,
(V)PAni, ()PTMS + PAni and () ODTMS + PAni.

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ECS Transactions, 43 (1) 57-64 (2012)

a)

5.5

5.5

5.0

5.0

4.5

4.5

4.0
3.5
3.0

4.0
3.5
3.0

2.5

2.5

2.0

2.0

1.5

1.5
-1 0 1 2 3 4 5
log (f / Hz)

-2 -1 0 1 2 3 4 5
log (f / Hz)

b)

80

80

70

70

60

60

50

50

40

d)

90

90

c)

6.0

log (|Z| / )

log (|Z| / )

6.0

40

30

30

20

20

10

10

0
-1 0

-2 -1 0 1 2 3 4 5
log (f / Hz)

1 2 3 4
log (f / Hz)

Figure 3. Bode plots for the AA2024 alloy with different coatings in 0.6 mol dm-3NaCl
aqueous solution. a) log |Z| - 1h immersed. b) phase angle 1h immersed. c) log |Z| - 60h
immersed. d) phase angle 60 h immersed: ()bare sample; ({)PTMS, (U)ODTMS,
(V)PAni, ()PTMS + PAni and () ODTMS + PAni.

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ECS Transactions, 43 (1) 57-64 (2012)

The Bode plots obtained for the double films show features related to both the coatings,
resulting in three capacitive domains, two related to the PAni and one to the SAM.
Additionally, it is clear from the results that the SAMs deposition previous to the PAni
coating improves the impedance of the resulting coating, mainly contributing to the barrier
effect. The same general features are observed for the coatings after 60 hours immersed.
However, in the case of the PTMS-PAni double film, the additional effect promoted by the
SAM is lost due to the lack of stability related to the small size of PTMS molecules. For the
samples coated only with ODTMS the total impedance is slightly bigger than that observed
for samples coated with ODTMS-PAni (Figs 2a and 2c, for frequencies smaller than 1 Hz).
However, from the behavior observed in the Fig. 1b the greater total impedance values is
expected from the ODTMS-PAni coating because its superior corrosion protection. These
controversy results can be related to changes in the polyaniline oxidation level, which can
decrease the impedance associated to the coating and still contribute to a superior corrosion
protection.
In the case of the AA2024 alloy, the same general characteristics commented for the
SAMs and PAni coatings for the AA1050 after 1 hour immersed in the corroding media are
also observed. However, SAMs deposition previous to the PAni coating does not improve
the total system impedance when compared to the PAni coating alone. Furthermore, in this
case the phase angle dependence on frequency for the double films does not exhibit the
features observed for the separate coatings, which suggests that the superior corrosion
protection behavior observed for the double films in the polarization curves are related to a
change in the corrosion protection mechanism. Additionally, after 60 hours of immersion
the double films still exhibits the same impedance behavior, which indicates the high
stability of such coatings.
These findings can be confirmed by the SEM micrographs showed in figure 4, where
the surfaces of the alloys, after the corrosion tests and removal of the coatings, can be
observed. Before the realization of the corrosion tests, both alloys showed a homogeneous
distribution of slots over the entire surface, resulting from the polishing process. After the
tests, the bare samples are clearly compromised by corrosion process, showing cracks in the
oxide layer and deposits of corrosion by-products. Still, the samples that were covered with
the bi-layers do not exhibit corrosion evidence.
Conclusion
The results lead to the following order of improved protection against corrosion of the
alloys: PTMS < ODTMS < PAni < PTMS + PAni < ODTMS + PAni. The bi-layer
ODTMS + PAni is the coating that showed higher positive shifts of Ecorr and higher values
of total impedance and suppression of the corrosion points. The superior properties of this
coating are related to the combination of the redox properties provided by the use of PAni
and the barrier effect added by the use of specific SAMs. There are also evidences that the
corrosion protection mechanism depends on the alloy nature.
Acknowledgements
The authors thank the Fundao de Amparo Pesquisa do Estado de So Paulo
(FAPESP) and Conselho Nacional de Pesquisa (CNPq), Brazil, for financial support.

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ECS Transactions, 43 (1) 57-64 (2012)

AA1050

AA2024

Bare Samples

PTMS+PAni

ODTMS+PAni

Figure 4.SEM images of the two alloys studied, with 1000x of magnification, after the
completion of the polarization curves in NaCl 0.6 mol dm-3 and removal of the coatings.

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