Anti-Corrosion Methods and Materials

Corrosion protective properties of coatings doped with inhibitors

Mansoureh Parsa Seyed Mohammad Ali Hosseini Zahra Hassani Effat Jamalizadeh

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Mansoureh Parsa Seyed Mohammad Ali Hosseini Zahra Hassani Effat Jamalizadeh , (2014),"Corrosion protective properties of
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Corrosion protective properties of coatings

doped with inhibitors
Mansoureh Parsa
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran

Seyed Mohammad Ali Hosseini

Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran and Department of New Materials, Institute
of Science and High Technology and Environmental Sciences, Graduate University of Advanced Technology, Kerman, Iran

Zahra Hassani
Department of New Materials, Institute of Science and High Technology and Environmental Sciences,
Graduate University of Advanced Technology, Kerman, Iran, and
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Effat Jamalizadeh
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran
Abstract
Purpose The purpose of this paper was to study the corrosion resistance of water-based sol-gel coatings containing titania nanoparticles doped
with organic inhibitors for corrosion protection of AA2024 alloy.
Design/methodology/approach The coatings were obtained using tetraethylorthosilicate, 3-glycidoxypropyltrimethoxysilane, titanium (IV)
tetrapropoxide and poly(ethylene imine) polymer as cross-linking agents. As corrosions inhibitors, 2-mercaptobenzoxazole and salicylaldoxime were
incorporated into the sol-gel for the improvement of the corrosion resistance. The corrosion protection performance of coatings was studied using
the potentiodynamic scan and the electrochemical impedance spectroscopy (EIS) methods. Atomic force microscopy was used to investigate surface
morphology of the coatings.
Findings The results indicated that doping the sol-gel coatings with inhibitors leads to improvement of the corrosion protection. The comparison
of doped coatings confirmed that corrosion protection performance of the sol-gel coatings doped with 2-mercaptobenzoxazole was better than for
the sol-gel coatings doped with salicylaldoxime. Also the EIS results verified self-healing effects for the sol-gel coatings doped with
2-mercaptobenzoxazole.
Originality/value This paper indicates 2-mercaptobenzoxazole and salicylaldoxime can be added as corrosion inhibitors to sol-gel coatings to
improve their corrosion protective properties for AA2024 alloy.
Keywords Corrosion, Corrosion inhibitors, Sol-gel coatings, 2-mercaptobenzoxazole, Salicylaldoxime, AA2024 alloy
Paper type Research paper

1. Introduction

One of the most widespread strategies for corrosion protection

of aluminum alloys is a complicated coating system, which
consists of at least three individual layers. The first thin layer is a
surface pretreatment step that provides additional long-term
corrosion protection of the substrate and good adhesion between
the metal substrate and following coats (Poznyak et al., 2008).
Chromate-based conversion coatings often are used for corrosion
control of these alloys. The usage of Cr-containing materials as
an anticorrosive pre-treatment for metallic surfaces has been
prohibited due to their carcinogen characteristics and their
substantial contribution to environmental pollution (Balaskas
et al., 2012; Reboul and Baroux, 2011).
As an environmentally safe alternative to chromates,
nanostructured sol-gel coatings have been reported to possess
good barrier properties (Roussi et al., 2011). Initially, sol-gel
inorganic metal oxide coatings were proposed for passive
corrosion protection. Subsequently, the synthesis of organicinorganic hybrid coatings has attracted the attention of
researchers because such coatings combine the properties of both
ceramic and organic components (Roussi et al., 2011;
Zheludkevich et al., 2006).
Another important aspect in designing coatings for
corrosion protection purposes is to decrease the volatile

Different kinds of aluminum alloys are widely used in the

aeronautical, architectural, transportation and manufacturing
industries, due to their high strength, toughness, light mass
and advantageous mechanical properties (Kartsonakis et al.,
2011; Li et al., 2007; Moutarlier et al., 2003). Aluminum and
its alloys, such as AA2024, have a natural tendency to form a
passive surface layer of Al2O3. However, this passivating layer
deteriorates in chloride-containing environments, which
results in pitting corrosion (Wang and Bierwagen, 2009).
Corrosion of aluminum alloys has an enormous economic
impact (Kartsonakis et al., 2012).

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Anti-Corrosion Methods and Materials

61/6 (2014) 416 422
Emerald Group Publishing Limited [ISSN 0003-5599]
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Anti-Corrosion Methods and Materials

Mansoureh Parsa et al.

Volume 61 Number 6 2014 416 422

organic content (VOC). Recently, water-based sol-gel systems

have been developed that offer the benefits of low volatile
organic compound contents, materials and processes
(Palanivel et al., 2005; Poznyak et al., 2008).
Sol-gel coatings provide dense barriers against corrosive
agents. However, small cracks, micropores and areas of low
cross-link density may exist in the coating that can allow the
diffusion of corrosive species such as water, oxygen and
chloride ions to the coatingmetal interface (Wang and Akid,
2007; Zheludkevich et al., 2005a). The incorporation of
corrosion inhibitors into the sol-gel films is one way by which
the corrosion protection self-healing abilities of the coating
can be enhanced (Roussi et al., 2011; Varma et al., 2009).
Organic and inorganic inhibitors have been used to improve
the corrosion protection properties of sol-gel coatings.
Inorganic inhibitors such as phosphates, vanadates, borates
and rare earth elements compounds such as cerium and
molybdenum salts have been shown to have a positive
influence on the corrosion protection of aluminum alloys
(Shchukin et al., 2006; Zheludkevich et al., 2005b; Kasten
et al., 2001). Most of the effective organic inhibitors are
compounds that contain hetero-atoms such as oxygen,
nitrogen, sulfur and phosphorus (Obot et al., 2011). The
corrosion mechanism of AA2024 was investigated and
reported in previous papers (Liu et al., 2005; Dimitrov et al.,
2000). Localized pitting corrosion begins at intermetallic
zones; the so-called secondary phase (S-phase). These zones
are composed of Al2MgCu and exhibit a cathodic potential
relative to the alloy matrix. Due to the presence of different
elements in this area, the native oxide film is weaker and more
defective. With the deterioration of this film in the S-phase
intermetallic phases, the chemical reactions of active aluminum
and magnesium from Al2MgCu particles with water occur.
These reactions lead to dealloying of S-phase, leaving
copper-rich remnants. Local increase of pH around the
S-phase particles along with enrichment of their surface with
copper result in shifting of the dissolution processes from
chemical to electrochemical. The cathodic reaction happens
on copper-rich remnants and, simultaneously, the oxidation of
magnesium and aluminum occurs at the anodic parts of the
S-phase (Yasakau et al., 2006).
Based on this information, organic compounds that are able to
form insoluble complex compounds with components of the
S-phase are suitable candidates to provide strong inhibiting
action (Lamaka et al., 2007).
In previous work, a new water-based sol-gel coating containing
titania nanoparticles for the protection of aluminum alloy
AA2024 against corrosion was developed (Parsa et al., 2013). In
the present work, salicylaldoxime and 2-mercaptobenzoxazole
were added as corrosion inhibitors to the hybrid sol-gel
formulations. No inhibitor had been studied previously as an
additive to this hybrid sol-gel formulation and, as far as is known,
there is no report that 2-mercaptobenzoxazole has been studied
as corrosion inhibitor for aluminum alloys.

the coupons were cleaned in 2-propanol, under ultrasonic

agitation, for 10 min (Parsa et al., 2013).
Sol-gel without inhibitor was prepared separately by controlled
hydrolysis of organosiloxane (sol1) and metal/organic (sol2)
parts. Sol(1) was prepared, with continuous stirring, by dropwise
addition of GPTMS (97 per cent pure, Merck) and TEOS (99
per cent pure, Merck), in a 3:1 molar ratio, to a 0.05 M solution
of acetic acid in doubly distilled deionized water. The resulting
solution was aged at room temperature under stirring for 2 h.
To prepare sol(2), acetylacetone and titanium(IV)
tetrapropoxide (TPOT) were mixed with a 1:3.5 molar ratio
under ultrasonic agitation for 30 min. Thereafter, acetic acid
and water were added under ultrasonic stirring for 60 min.
Finally, sol(1) and sol(2) were mixed and this mixture was
stirred under ultrasonic agitation for 1 h. Next, 0.14 g of the
hyperbranched polymer poly(ethylene imine) (PEI) was
added in 8 mL solution and the solution was diluted by a
factor of 1.5. This mixture was stirred under ultrasonic
agitation for an additional 1 h. The final sol was agitated at
room temperature for 15 h (Parsa et al., 2013). Furthermore,
for preparing sol-gels containing corrosion inhibitors,
2-mercaptobenzoxazole and salicylaldoxime were dissolved
into the prepared solution prior to the addition of the
cross-linking polymer (PEI) (Roussi et al., 2011).
A dip coating process (involving dipping of substrates into
the sol for 100 s, followed by controllable ascension with a
speed of 10 cm/min) was used to coat the AA2024 panels. The
samples were dried at room temperature for 24 h and then
heated at 120C for 1 h (Parsa et al., 2013). The prepared
coatings are listed in Table I.

2.2 Characterization of coatings

Harrisons solution (0.35 weight per cent (NH4)2SO4 0.05
weight per cent NaCl) was used as the electrolyte because this
mixture emulates the atmospheric conditions of an aircraft
(Voevodin et al., 2006). The corrosion behavior of the coated
aluminum specimens was examined at room temperature
using potentiodynamic scan (PDS) and electrochemical
impedance spectroscopy (EIS) with an Auto-lab 302N
potentiostat and Nova 1.6 software. These measurements
were undertaken in the Harrisons solution using a
three-electrode electrochemical cell consisting of a platinum
electrode as a counter electrode, a saturated calomel electrode
as a reference electrode and aluminum AA2024 sample with
an exposed area of 1 cm2 as a working electrode.
The surface morphology of the coatings was assessed by
atomic force microscopy (AFM). AFM studies were performed
using Dualscope/Rasterscope C26, DME, Denmark, in a
noncontact mode, with a silicon tip.
Table I Coatings prepared

2. Experimental procedures
2.1 Development of coatings
AA2024 aluminum alloy was used as the substrate. The size of
test coupons was 1 1 cm2 and each was 0.5 cm in thickness.
The samples were abraded with emery paper to 2,500 grit and
417

Coating code

Inhibitor

TMSNAP
TMSNAP-MBO
TMSNAP-Sal

2-mercaptobenzoxazole
Salicylaldoxime

Corrosion protective properties

Anti-Corrosion Methods and Materials

Mansoureh Parsa et al.

Volume 61 Number 6 2014 416 422

3. Results

Figure 2 Bode plots for bare AA2024 alloy and coated AA2024
alloy after 72 h of immersion in Harrisons solution

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3.1 Potentiodynamic scan

Potentiodynamic polarization curves for bare AA2024 alloy after
1 h immersion and coated samples with TMSNAP,
TMSNAP-MBO and TMSNAP-Sal after 36 h of immersion in
Harrisons solution are shown in Figure 1. The corrosion
parameters, corrosion potential (Ecorr) and corrosion current density
(icorr), are recorded in Table II. As is evident, coated specimens with
TMSNAP, TMSNAP-MBO and TMSNAP-Sal sol-gels have
lower corrosion current compared to bare alloy. Furthermore, a
negative shift is observed for the corrosion potential of coated
AA2024 samples in comparison with uncoated alloy.

3.2 Electrochemical impedance spectroscopy

The corrosion behavior of coatings undoped and doped with
inhibitors in the Harrisons solution was studied using EIS.
Figure 2 presents the EIS Bode plots, in frequency range from
102 to 105 Hz, for the sol-gel coatings undoped and doped
with 2-mercaptobenzoxazole and salicylaldoxime after 72 h of
immersion. The impedance spectrum of bare AA2024
substrate, after 72 h of immersion, is presented as reference.
As is evident, in low-frequency range, the impedance values
for coated systems were significantly higher than the
impedance values measured for the bare alloy, and also the
low-frequency impedance of the sol-gel coatings doped with
inhibitor was higher than undoped sol-gel coating.
Figures 3 and 4 illustrate the evolution of the impedance
spectra for TMSNAP-MBO and TMSNAP-Sal coatings,
respectively, after different periods of immersion in the
Harrisons solution. In general, the impedance values at low
frequency decreased with time in both Figures 3 and 4, but for
the impedance spectra of TMSNAP-MBO, a remarkable

Figure 3 Bode plots for coated AA2024 alloy with TMSNAP-MBO

sol-gel after different periods of immersion in Harrisons solution

Figure 1 Polarization plots for bare AA2024 alloy after 1 h and

coated AA2024 alloy after 36 h of immersion in Harrisons solution

Table II Electrochemical parameters for bare AA2024 alloy after 1 h and coated AA2024 alloy after 36 h of immersion in Harrisons solution from
polarization curves
Electrochemical parameters
2

icorr (A/cm )
Ecorr (mV)

Bare alloy
6

3.48 10
463

TMSNAP
8

6.49 10
625

418

TMSNAP-MBO
8

4.10 10
589

TMSNAP-Sal
4.52 108
633

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Figure 4 Bode plots for coated AA2024 alloy with TMSNAP-Sal

sol-gel after different periods of immersion in Harrisons solution

Figure 5 AFM images of sol-gel coatings

increase of impedance value at low frequency can be observed

from 192 to 384 h of immersion.
3.3 Morphology of the films
AFM was used to characterize the surface topography of the
coated substrates. Figure 5 shows the AFM images of coatings
undoped and doped with inhibitors. The surface morphology
of coatings was uniform with an absence of any defects. These
images reveal the presence of nanoparticles on all prepared
coatings. The size of these particles was in the range 14-50
nm. A few particles had larger diameters and seemed to result
from agglomerates of smaller ones (Zheludkevich et al.,
2005b).

4. Discussion
As an important aspect in designing environmentally safe
coatings for corrosion protection of alloys is the decrease of the
VOC, water-based sol-gel coatings have been developed for use
on aluminum alloys. A new water-based sol-gel coating containing
titania nanoparticles for the protection of AA2024 alloy against
corrosion was prepared previously (Parsa et al., 2013). To increase
the corrosion protection properties of this coating, in present work,
salicylaldoxime and 2-mercaptobenzoxazole, as corrosion inhibitors,
were added to the hybrid sol-gel formulations and the formation of
nanoparticles all over the coatings was confirmed using AFM.

The results presented in Figure 1 show that coated AA2024

samples had lower corrosion currents, compared to bare alloy,
indicating protection of the alloy against corrosion (Roussi
et al., 2011). Comparison of the results of the polarization
curves for undoped and doped coatings indicates that the
addition of 2-mercaptobenzoxazole and salicylaldoxime to the
sol-gel system did not seem to have any significant negative
effect on the barrier properties of the coatings (Pirhady
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Volume 61 Number 6 2014 416 422

Tavandashti et al., 2011). Furthermore, the observed negative

shift in the corrosion potential of coated AA2024 samples
indicated their ability to provide superior inhibition of the
cathodic process, especially as compared to their effect on the
anodic process (Shahidi et al., 2011).

intermediate oxide layer has been healed with time, indicating

the self-healing effect of inhibitor on corrosion spots (Shi et al.,
2010; Tavandashti and Sanjabi, 2010).
After a long exposure period of 576 h, the anticorrosive
properties of the film reduced as the total impedance value
decreased and a new time constant appeared at low
frequencies, which was attributed to the electrical double
layer, which is a sign of the beginning of the corrosion process
(Zheludkevich et al., 2005b; Tavandashti and Sanjabi, 2010).
According to Figure 4, after 72 h of immersion, the
impedance spectra of TMSNAP-SD coating showed time
constants in the high-frequency region similar to that of
TMSNAP-MBO. This feature probably can be ascribed to the
sol-gel layer capacitance and represents the barrier properties
of the coating. In addition, in the middle-frequency range, two
time constants can be observed; one due to the formed
aluminum oxide and the other due to a layer that is formed
because of the presence of the inhibitor (Balaskas et al., 2011;
Kartsonakis et al., 2011). Three resistive parts also could be
observed in the impedance spectra after 72 h of immersion.
The solution resistance appears at high frequency, and the
observed resistive part at middle frequency is characteristic of
the sol-gel film. The EIS plots in Figure 4 show that the pore
resistance of the sol-gel film decreased with immersion time.
This can be the result of the development of defects such as
pores and cracks in the coating when exposed to the corrosive
environment (Balaskas et al., 2011). The third resistive part
was related to the resistive response of the intermediate
oxide layer and was evident in the range 101-102 Hz and
results from cracks that are formed in the intermediate
oxide layer (Zheludkevich et al., 2005b). After 384 h of
immersion, the existence of a third time constant
corresponding to the electrical double layer was not visible,
showing that the TMSNAP-SD coatings have good
resistance against pitting corrosion (Tavandashti and
Sanjabi, 2010), but after 576 h of immersion, the
impedance value at low frequency exhibited a marked
decrease, indicating degradation of the sol-gel coating (Shi
et al., 2010).
Overall, the impedance values at low frequency for the
sol-gel coatings doped with 2-mercaptobenzoxazole were
higher than the sol-gel coatings doped with salicylaldoxime
during the same immersion times, indicating the better
corrosion protection properties of TMSNAP-MBO coating
compared to TMSNAP-Sal coating. The results indicate that
the sol-gel coatings doped with inhibitors, especially
TMSNAP-MBO, provided significant protection against
corrosion of the AA2024 alloy in Harrisons solution after long
immersion times, confirming the results of previous studies
(Kartsonakis et al., 2011; Balaskas et al., 2011; Tavandashti
and Sanjabi, 2010; Shi et al., 2010).

4.1 Electrochemical impedance spectroscopy

In EIS spectra, the number of time constants can be judged
from frequency-phase angle diagram of Bode plots by the
number of peaks on the Bode trace. The degradation of the
sol-gel coatings can be evaluated using the total impedance
(i.e. the low-frequency intercept value, frequency 0.01 Hz)
and the occurrence of next peak with time (Shi et al., 2010).
Figure 2 showed that impedance values at low frequency for
the coated systems were significantly higher than for the bare
alloy, evidencing the barrier properties of these coatings.
Moreover, the sol-gel coatings doped with inhibitors have
higher low-frequency impedance values compared to undoped
sol-gel coating, which indicates that corrosion protection
properties are highly improved for the TMSNAP-MBO and
TMSNAP-Sal sol-gel coatings, compared to the TMSNAP
sol-gel coating (Zheludkevich et al., 2006).
In Figure 3, the phase angle plots present time constants in
the high-frequency region, which can be ascribed to the sol-gel
film capacitance, and reveal that the coating behaves as a
barrier layer (Balaskas et al., 2011; Kartsonakis et al., 2011).
Furthermore, in the middle-frequency range, the coating
presents two time constants, one due to the presence of the
intermediate oxide film at the metal/coating interface and the
other due to the formatted complex between the inhibitor and
the aluminum substrate (Kartsonakis et al., 2011).
Before starting the corrosion process, the time constant at
low frequencies corresponding to the corrosion process is
absent. After long immersion times, the signs of the corrosion
process were detected by developing additional time constants
at low frequencies (Zheludkevich et al., 2006; Zheludkevich
et al., 2005b).
The resistive parts also are observed in the impedance
spectra with time of immersion. The first appears at high
frequency, describing the resistance of the solution, and the
next appears in the medium-frequency range, and has been
attributed to the pore resistance of the sol-gel layer (Raps
et al., 2009; Tavandashti and Sanjabi, 2010). As long as the
oxide film is intact, the resistive response at low frequencies,
reflecting the resistance of the intermediate oxide layer, almost
does not appear. However, when cracks occur in the
intermediate oxide layer, the electrolyte can ingress directly to
the substrate, forming conductive pathways and causing the
low-frequency resistive response (Zheludkevich et al., 2005b).
It can be seen that the impedance value at low frequency
decreases slightly with time from 72 to 192 h of immersion.
After 192 h of immersion, a resistive response attributed to the
intermediate oxide layer appears, but after 384 h of
immersion, this resistive response disappears. As described
before, the resistive response in the intermediate oxide layer is
due to formation of cracks and pores in this layer, which
appeared after 192 h of immersion and disappeared after 384
h. Additionally, the low-frequency impedance response
decreased with time of immersion up to 192 h, but up to 384
h, it increased significantly. It would seem that the

4.2 Inhibition of 2-mercaptobenzoxazole and

salicylaldoxime
As noted above, the corrosion of AA2024 alloy starts from the
intermetallic zones that are composed of Al2MgCu particles.
The chemical and electrochemical dissolution of aluminum
and magnesium from Al2MgCu particles occurs at the initial
stages of the corrosion process, which leads to dealloying of
intermetallic zones enriching them in copper. Due to the
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Mansoureh Parsa et al.

Volume 61 Number 6 2014 416 422

chemical dissolution of copper, with consequent electrochemical

redeposition, local corrosion attack develops. Thus, an effective
strategy of inhibition of localized corrosion on the AA2024 alloy
can be based on the suppression of S-phase dealloying and
copper redeposition. (Lamaka et al., 2007).
Salicylaldoxime is able to form insoluble complexes with Al
and Cu. The result of this process is the formation of
water-insoluble complex layers on the entire metal surface and
on the active sites of AA2024 alloy. This adsorptive protective,
inhibitor-containing layer on the surface of the alloy, leads to
passivation of active intermetallic zones, due to the prevention
of Mg, Al and Cu dissolution. Moreover, the insoluble chelate
layer prevents adsorption of aggressive chloride ions onto the
surface of the alloy (Lamaka et al., 2007).
As far as can be ascertained, 2-mercaptobenzoxazole has
not been mentioned previously in the technical literature as an
inhibitor of aluminum corrosion processes. However, its use
as a good inhibitor for copper in chloride-containing
environments has been studied (Fleischmann et al., 1985;
Musiani et al., 1987; Yan et al., 2000). As previously
mentioned, organic compounds can form a complex with
copper and thereby block its dissolution, effectively preventing
localized corrosion on AA2024 alloy. In chloride-containing
media, 2-mercaptobenzoxazole forms a three-dimensional
compact cuprous complex film on the surface that retards the
corrosion process (Yan et al., 2000). Thus, it seems that the
inhibiting action of 2-mercaptobenzoxazole is a consequence
of suppression of Cu dissolution from the intermetallic zones.

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performance of AA2024-T3 in a 0.5 M NaCl solution,
Progress in Organic Coatings, Vol. 53 No. 2, pp. 153-168.
Parsa, M., Hosseini, S., Jamalizadeh, E. and Saheb, V.
(2013), Preparation and corrosion protective properties
of titania-containing modified self-assembled nanophase
particle (TMSNAP) sol-gel on AA2024 aluminum alloy,
Materials and Corrosion, Vol. 64 No. 9, pp. 821-830.

5. Conclusions
Taken together, addition of 2-mercaptobenzoxazole and
salicylaldoxime as corrosion inhibitors to sol-gel coatings
significantly improved the corrosion protection properties of
the coatings.
The sol-gel coating doped with 2-mercaptobenzoxazole
exhibited better corrosion protection than did the sol-gel
coating doped with salicylaldoxime. Moreover, the coating
doped with 2-mercaptobenzoxazole indicated well-defined
self-healing effects that were confirmed from the EIS data.
Therefore it was concluded that 2-mercaptobenzoxazole can
be added to coating system as an appropriate corrosion
inhibitor for AA2024 aluminum alloy.
The obtained doped sol-gel coatings can provide long-term
corrosion protection and can be prospective candidates for the
development of new environmentally friendly pretreatments.

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Corresponding author
Seyed Mohammad Ali Hosseini can be contacted at:
s.m.a.hosseini@mail.uk.ac.ir

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