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Progress
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xxx (2015)
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J. Carneiro et
al. / Progress
in Organic
Coatings
xxx (2015)
xxxxxx

Contents lists available at ScienceDirect

Progress in Organic Coatings


j o ur na l ho me pa ge:
w w w.e l s e v i e r. c o m / l o c a t e / p o r g c o a t

Review

Chitosan as a smart coating for corrosion protection of aluminum


alloy 2024: A review
J. Carneiro, J. Tedim , M.G.S. Ferreira
Department of Materials and Ceramic Engineering, CICECO-Aveiro Institute of Materials, University of Aveiro, 3810-193 Aveiro, Portugal

a r t i c l e

i n f o

Article history:
Available online xxx
Keywords:
Chitosan
Coatings
Corrosion protection
Smart coating
AA2024

a b s t r a c t
In this work we review results obtained using chitosan as a coating to protect aluminum alloy 2024.
Different inhibitors were added to the matrix, interaction between inhibitor and functional groups
from chitosan investigated and functionalization of chitosan performed in the bulk, as well as at the
coating/solution interface to improve the barrier properties. The obtained systems were characterized
by proton-nuclear magnetic resonance (1 H NMR), Fourier transform infrared spectroscopy (FTIR) and
scanning electron microscopy (SEM). The protective performance was monitored using electrochemical impedance spectroscopy (EIS) and the scanning vibrating electrode technique (SVET). Overall, the
obtained results support the possibility of using inhibitor-loaded chitosan systems to protect metallic
substrates, either as components in multi-layer coatings systems, or as free-standing lms.
2015 Elsevier B.V. All rights reserved.

Contents
1.
2.

3.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.Results
. . . . . . . and
. . . . discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.2.1.
. . . . . . Chitosan
.....
for protection of aluminum early works . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . corrosion
.
2.2.
Active
protection using cerium (III) nitrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.Functionalization
.......
2.3.
of CTS matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . corrosion
...
2.4.
Active
protection using organic MBT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . a suitable coating for corrosion protection? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Chitosan:
. . . . . . and
. . future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions
.Acknowledgements
.........
......................................................................................................................
.References
. . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.............

1. Introduction
The introduction of new environmental regulations restricting
the use of well-established corrosion inhibitors and the need to
decrease VOC emissions has prompted the need to develop alternative systems to prevent corrosion. In this context, water-based
coatings based on renewable resources appear as good and
promis- ing alternatives to the existing organic-based coatings
[1,2].
Chitosan (referred hereafter as CTS) is a linear copolymer
of -(1-4)-2-amido-2-deoxy-d-glucan (glucosamine) and -(1-4)2-acetamido-deoxy-d-glucan (N-acetylglucosamine) that can be

Corresponding author. Tel.: +351 234370255; fax: +351 234378146.


E-mail address: joao.tedim@ua.pt (J. Tedim).

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produced from chitin by means of a partial alkaline deacetylation. Chitin is the second most abundant polysaccharide in Nature,
after cellulose, and is available worldwide. When CTS is dissolved
in a dilute acidic medium, the amine groups become protonated
and the ensuing positive charges confer polyelectrolyte-like behavior to the macromolecule. Its unique physicochemical properties
include biocompatibility, antimicrobial activity, biodegradability
and excellent lm-forming ability, which have attracted scientic
and industrial interest in many elds: biotechnology, pharmaceutics, biomedicine, packaging, wastewater treatment, cosmetics and
food science, among others [39]. Also, CTS is a suitable candidate
for application as protective coating against corrosion of metallic
substrates, due to its specic properties such as good lmforming ability, superior adhesion to metallic surfaces and
versatility asso- ciated with the easiness of chemical
functionalization.

http://dx.doi.org/10.1016/j.porgcoat.2015.03.008
0300-9440/ 2015 Elsevier B.V. All rights reserved.

Please
Please
citecite
thisthis
article
article
in press
in press
as: as:
J. Carneiro,
J. Carneiro,
et al.,
et al.,
Chitosan
Chitosan
as aassmart
a smart
coating
coating
for for
corrosion
corrosion
protection
protection
of aluminum
of aluminum
alloy
alloy
2024:
2024:
A A
review,
review,
Prog.
Prog.
Org.Org.
Coat.
Coat.
(2015),
(2015),
http://dx.doi.org/10.1016/j.porgcoat.2015.03.008
http://dx.doi.org/10.1016/j.porgcoat.2015.03.008

The application of CTS as a coating for metallic structures has


been the topic for several studies in recent years, mainly for
magne- sium [10,11] and steel alloys [1215]. However, works
reporting the use of chitosan for aluminum and corresponding
alloys are scarce.
Aluminum alloy 2024-T3 has been used in the aerospace due
to its excellent weight-to-strength ratio [16]. The mechanical
prop- erties of this alloy are enhanced by the presence of
intermetallic particles, which are also responsible for a higher
susceptibility toward localized corrosion. As a result, there is a
strong need to develop environmentally
friendly coatings
capable of providing protection against the aggressiveness of the
surrounding environ- ment.
The present review starts by describing early works on the
appli- cation of CTS for protection of aluminum substrates. Then,
the main highlights of our work focused on corrosion protection
of AA2024 using CTS as a polymer reservoir for different
corrosion inhibitors are presented [1720]. Finally, a critical
discussion of the results and future perspectives for use of CTS in
industrial applications are addressed.
2. Results and discussion
2.1. Chitosan for protection of aluminum early works
The rst works reporting the use of CTS for protection of aluminum alloys focused on the decrease of permeability to water,
in other words for the enhancement of the barrier effect against
ingress of aggressive electrolyte species.
The rst work found in the literature dates from 2000, by
Sugama and Cook [21]. In this work, chitosan was modied
with a synthetic polymer (poly(itaconic acid), PIA) to promote
the crosslinking between chitosan chains. Films were obtained by
dip coating on AA6061-T6 and the protection of the substrate
found to rely on different aspects highlighted by the authors:
polymer chem- istry (presence of hydrophobic amide bonds), less
susceptibility to moisture due to grafting and crosslinking (Fig.
1), and adhesion properties promoted by the formation of a
COO Al linkage. From all CTS:PAI ratio tested, coatings prepared
with CTS:PIA ratio of
80:20 revealed the highest pore resistance determined by
electro- chemical impedance spectroscopy (EIS), and salt-spray
resistance for 694 h.
More recently, Lundvall and colleagues reported the application of CTS for protection of aluminum alloy 2024 [22]. In
this study, the metallic substrate was rst anodized to promote
adhesion of the subsequently dip coated chitosan lm (Fig. 2). The

Fig. 1. Changes in contact angle of a water droplet on surfaces of coating lms


made with: () 100:0; ( ) 0:100; ( ) 30:70; ( ) 50:50;
( ) 70:30; ( ) 80:20; (X)
90:10 ratios as a function of exposure in water at 25 C [21].

Fig. 2. Transmission electron micrograph showing an ultramicrotomed section of


the anodized AA-2024-T3 coated by chitosan [22].

resulting systems were subsequently immersed in copper sulfate


and acetate solutions with different concentrations for 24 h, to
reduce the permeability of CTS lms. Open circuit potential
(OCP) measurements showed that incorporation of Cu2+ in the
chitosan coating shifts the initial OCP in the anodic direction
with respect to the unmodied system. Moreover, CTS lms
immersed in copper acetate solutions performed better than the
copper sulfate homologues. The authors claimed this was due to
differences in pH between the two salt solutions, which affect
CTS solubility during copper incorporation (higher acidity
corresponds to higher CTS solubility). The visible spectra of CTS
modied with Cu2+ from solutions at different pH
were
interpreted considering coordina- tion of Cu2+ with amino groups
from CTS, thereby suggesting that the decrease in permeability
of modied CTS was due to cross linking between copper ions
and the CTS structure.
2.2. Active corrosion protection using cerium (III) nitrate
The works presented in Section 2.1 rely upon improvement of
barrier effect in the absence of corrosion inhibitors. In the recent
work of Zheludkevich and colleagues [18], Ce3+ was used as a corrosion inhibitor and incorporated in CTS for protection of AA2024.
The coating system comprised a CTS pre-layer, overcoated with a
hybrid solgel lm. In this case, CTS was used as a polymer reservoir for the corrosion inhibitor, being intrinsically associated to
the active corrosion protection and healing of defects, whereas
the hybrid solgel top layer conferred a physical barrier effect
against ingress of aggressive species. (The synthesis and properties
of these protective solgel lms were described elsewhere [23]).
Cerium (III) nitrate was added directly to the CTS solution in
1% (v/v) aqueous acetic acid, resulting in smooth and uniform
coat- ings [18]. The FTIR spectra showed that a new band
occurring
at 530 cm1 is probably associated to the CeN vibrations arising
from the coordination of Ce(III) with nitrogen atoms of the
chitosan macromolecules.
Fig. 3 depicts the cross-sectional micrographs of the bilayer
coat- ing with CTS-doped pre-layer, overcoated by solgel. The
presence of the CTS layer is visible between the metallic
subtract and the solgel layer, with an average thickness of 1
m. The EDS map clearly shows the presence of Ce3+ inside the
CTS layer. Moreover, the inhibitor immobilization within the prelayer is evident, without signicant penetration into the solgel coating and CTS lms
display a good adhesion to both metallic surface and hybrid sol
gel layer, without any signs of delamination at either interface.

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J. Carneiro
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Fig. 3. SEM cross-section of bi-layer coatings with Ce-containing chitosan (a and


b) and EDS map of the marked zone (c) [18] (Reproduced by permission of The
Royal Society of Chemistry).

The electrochemical impedance spectroscopy (EIS) spectra of


aluminum alloys substrates coated with CTS are presented in
Fig. 4(a). Two well dened relaxation constants are detected at
intermediate (101 102 Hz) and low frequencies (101 100 Hz),
with the rst being assigned to the natural oxide layer and the
second associated with corrosion processes. The oxide resistance
is signicantly low, leading to increased double layer capacitance
(3.7 104
cm2 for CTS after 4 h of immersion). Usually, the occurrence of a time constant at high frequencies for coated samples is

ascribed to the barrier effect provided by the coatings. However, the


inexistence of this time constant in the EIS spectra is an indication
of CTS coatings exhibiting poor barrier properties.
After 2 days of immersion in 50 mM NaCl solution, the CTS coating showed a pronounced decrease of impedance magnitude, at
intermediate (101 102 Hz) and low frequencies (101 100 Hz). At
this point, the time constants observed can be ascribed to
corrosion- and mass transport-controlled processes. The
response of native aluminum oxide layer is no longer detected
due to heavy corrosion attack. Nevertheless, the visual analysis of
the systems show some improvements for samples coated with
CTS when compared with bare AA2024, as observed in Fig. 4(d)
and (e).
In the presence of inhibitor Ce3+ the results are remarkably
different. For short immersion times (1 h) the impedance in the
low frequency range is lower than in the case of unloaded CTS,
which can be related with the complexation of Ce3+ cations by CTS
functional groups. This may restrict the availability of functional
groups to interact with the metallic substrate, thereby resulting in a
decrease of adhesive properties, or favor the increase of water content within the CTS lms, thus increasing permeation by
electrolyte species. After some immersion time, the impedance
values start to rise by about one order of magnitude, reaching a
maximum after 4 h of immersion, as presented in Fig. 4(b). For
longer immersion times, the impedance magnitude decreased
slightly and becomes stable for at least 2 days. This behavior
clearly points toward self-healing effect of Ce-doped CTS lms,
being supported by visual analysis of the samples that show no
clear signs of corrosion after 2 days of immersion (Fig. 4(f)).
The application of a second layer consisting of a hybrid solgel
system as a top-coat renders considerable improvement in the
barrier proprieties of protective coating, as inferred from the EIS
analysis (Fig. 4(c)), with one additional time-constant observed at
104 Hz. However, even with this extra barrier, the resistance of the
oxide lm on the metal/CTS interface was comparable to that of
CTS coating alone [18].
When the solgel layer covers the Ce-containing CTS layer, a
clear self-healing effect provided by the release of Ce3+ into the
CTS/metallic interface is observed in the EIS spectra. After 48 h of
immersion, the resistance of the oxide layer is one order of
magni- tude higher for the system containing cerium (Fig. 4(b)),
providing considerable better results than in the absence of
inhibitor.
To infer on the self-healing effect of CTS coatings loaded with
Ce3+ the SVET method was employed. This method allows the
quan- tication of local corrosion current densities in microconned defects of
protective coatings during immersion
corrosion tests, in a 50 mM NaCl solution. Two articial defects,
around 200
m in diameter, were made on the sample surface,
using a metallic needle,
before the beginning of the immersion tests, simulating servicelife damage (Fig. 5).
The best results, from a corrosion protection perspective, were
obtained with CTS Ce/solgel bilayer system. In the beginning
of immersion, well-dened anodic and cathodic electrochemical
activity could be observed at defects. Several hours later, the anodic
currents reduced markedly in these sites, which indicates that
metal dissolution had become very much limited, situation that
remained for longer immersion times [18]. The decrease in electrochemical activity can be explained by the corrosion inhibiting
effect provided by Ce3+ [24,25], with the formation of hydroxide
deposits blocking the corrosion activity under CTS coating. Nevertheless, the cathodic activity still detected in the defects can be
due to the insufcient amount of Ce3+ available at these sites.
2.3. Functionalization of CTS matrix
One important characteristic that denes the performance
of anticorrosion coatings is the barrier effect against ingress of

Fig. 4. Bode plots obtained after different immersion times in 0.05 M NaCl on AA2024 coated with a blank chitosan layer (a), a Ce-doped lm (b) and Ce-doped lm
overcoated with a hybrid solgel layer (c). Optical photographs of the bare AA2024 (d) and coated with undoped chitosan (e), Ce-containing chitosan (f), and Cecontaining chitosan with additional solgel top layer (g). The photos were taken after 1 day (d and e) and 2 days (f and g) of immersion in 0.05 M NaCl [18] (Reproduced
by permission of The Royal Society of Chemistry).

water and electrolyte. CTS, due to its chemical structure, is highly


hydrophilic, thereby posing challenges to its use as a truly barrier. To circumvent the lack of barrier, CTS was functionalized
by a reaction with an epoxy-based reagent, glycidyl 2,2,3,3tetrauoropropyl ether (GTFE) [17]. In addition to the bands of
CTS, the FTIR spectrum of GTFE CTS exhibited well dened bands
at 830 cm1 normally attributed to the aliphatic ether linkage, and
weak bands at 1202 and 1230 cm1 associated to the C F bonds
(Fig. 6(a)) [26]. Also, a decrease
in the intensity of the primary
amine
at band
1590 corresponding
cm1 was veried
together
withamine
a small
increaseband
in
the
to the
secondary
at
1640 cm1 , related
to the functionalization of the amine
group.
The 1 H NMR (CD3 CO2 D 1%/D2 O) spectrum (Fig. 6(b))
supports the functionalization of CTS with GTFE, and allows the
determina- tion of the degree of substitution (DS). In addition to
the signals ascribed to the CTS structure, GTFE CTS presents new
resonances at = 3.3 ppm and = 4.6 ppm (s, protons of
uorinated side chain), = 6.57.0 ppm (t, corresponding to the
proton coupled with neigh- boring uorine atoms) Fig. 6.
GTFE CTS preserved all the CTS properties and was applied
onto AA2024 in the same way as unmodied CTS, giving
smooth and uniform coatings, with only a slight increase in water
contact angle values. The
results obtained from EIS
measurements show that the GTFE CTS has
low
barrier
properties, similarly to the unmod- ied CTS. As in the case of
CTS two well-dened time-constants are
detected at
intermediate frequencies (101 102 Hz) and at lowfrequencies (101 100 Hz). In fact, GTFE CTS shows even worse
performance during the rst hours of immersion when compared
to

the unmodied CTS. However, after 1 day of immersion, GTFE CTS


exhibits a response superior to CTS [17].
The effect of loading content of corrosion inhibitor in CTS was
surveyed as well. When different amounts of Ce3+ are added to
unmodied CTS, different responses are obtained. The best results
obtained for small immersion times correspond to the coating
loaded with lower amount of inhibitor (1 wt.%), and not the one
prepared with highest Ce3+
concentration. This may be
interpreted by opposing factors that come into play when Ce3+ is
added to CTS. On one hand Ce3+ is a corrosion inhibitor providing
active corro- sion protection functionality to the system, but on
the other hand the complexation of Ce3+ may affect the degree
of water and/or limit the number of functional groups available to
promote adhe- sion between CTS and the surface. Nevertheless,
for long periods of immersion the coating with most concentrated
Ce3+ (CTS Ce 10%) displays the best active corrosion protection
performance, with a continuous increase of the oxide lm
resistance (Fig. 7) [17].
EIS measurements showed that the presence of cerium (III)
nitrate in GTFE CTS leads to an improvement of the corrosion protection. Moreover, GTFE CTS presents slightly better results when
compared with unmodied CTS, both in the presence of inhibitor,
after one day of immersion in 50 mM NaCl solution [17].
2.4. Active corrosion protection using organic MBT
As shown previously, the use of cerium (III) nitrate in CTS-based
coatings led to improvements in the corrosion protection of aluminum alloy 2024. In spite of successful functionalization with

Fig. 5. Optical micrograph (a) and SVET maps obtained on AA2024, coated with Ce-containing chitosan and sol-gel bilayers after different immersion times in 0.05 M NaCl
solution: 1.5 h (b), 5 h (e) , 40 h (f) and 70 h (40 h in 0.05 M NaCl + 30 h in 0.5 M NaCl) (g). Selected current proles from map in panel b (c) and maps in panels e, f and g
(d) [18] (Reproduced by permission of The Royal Society of Chemistry).

uorine-based groups, the modied CTS matrix did not reveal


truly physical barrier properties against electrolyte species. At the
same time, the use of water soluble inhibitors such as cerium (III)
nitrate has an effect on the propensity of the matrix to entrap
more water and thus be more open to the ingress of electrolyte.
More recently, the organic inhibitor 2-mercaptobenzothiazole
(MBT) was used within CTS matrix and the corrosion protection
conferred to AA2024 evaluated [19,20]. MBT is fairly insoluble in
water, and the incorporation of this inhibitor in CTS lms was
made in a mixture of ethanol/water to increase MBT solubility, and
in this way obtain coatings. The resulting systems exhibited a
yellowish coloration, which was attributed to presence of MBT.
Additionally, the incorporation of MBT was followed by FTIR.
Bands ascribed to
MBT at 565 and 599 cm1 , associated with torsion of the
aromatic
ring, and signals at 14281594 cm1 assigned to C C stretching
and to N H bending were detected in the
spectrum of CTS MBT.
Furthermore, bands occurring at 669 cm1
correspond to the C S
stretching, while bands at 10151076 cm1 are 1attributed 1
to C S
stretching in the S C S, and bands at 1285 cm , 1319 cm and
1248 cm11are assigned to C N stretching. A strong signal appears
at 745 cm associated with the CH and NH wagging [27]. There
was no additional vibration mode that could be associated with
the interaction between CTS and MBT structural groups. This
may be due to the large amounts of MBT trapped within the CTS
matrix that do not chemically interact with CTS, possibly
overlapping and masking any vibration modes related with
CTS/MBT interaction.
One of the most interesting characteristics ascribed to CTS
is its pH-dependent solubility by protonationdeprotonation of
amine substituents. This fact becomes relevant if one considers
the pH-dependence of corrosion processes and the need to provide inhibitors under such conditions. Therefore, the
combination

of CTS and MBT may lead to some sort of pH-dependent response.


Accordingly, the release of MBT from CTS was investigated in conditions representing corrosion-relevant triggers: NaCl and media
with different pH (Fig. 8). The release of MBT from CTS was found
to be preferential at pH 10, followed by pH 3. The lowest release
extent was obtained in distilled water (pH 6.4) and in NaCl
solution (pH 5.5). These ndings were interpreted in the following
way [19]: for low pH the CTS solubility dominates, allowing the
release of entrapped MBT, whereas for high pH the MBT solubility
displayed an important role since chitosan is insoluble in these
conditions. Under neutral conditions (distilled water and NaCl
solution) the limited release of MBT could be associated with low
solubility of both CTS and MBT.
CTS and GTFE CTS loaded with 1% and 10 wt.% MBT were
applied by dip-coating and the resulting coatings characterized by
SEM (not shown) [20]. The CTS layer applied onto AA2024
samples appears as a thin lm, following the morphology of the
alloy microstructure. With the addition of MBT, the CTS-coatings
morphology becomes grainy, presenting similar morphology to
the MBT powder. The EIS spectra of systems loaded with MBT,
Fig. 9(a), show two overlapped relaxation
constants at intermediate (101 102 Hz) and low
frequencies (101 100 Hz), whereas for undoped CTS coatings the
detected relaxation processes are well separated, exhibiting lower
impedance values than MBT-containing CTS coatings.
After 7 days of immersion (Fig. 9(b)) there are no signicant
changes for coatings with MBT, whereas in the absence of MBT the
impedance values at intermediate and low frequencies decreased
remarkably with respect to the initial immersion times. The
corre- sponding time constants are now ascribed to corrosionand mass transport-controlled processes. The EIS results are in
agreement with visual analysis of samples depicted in Fig. 9(c).

Fig. 6. a) ATR-FTIR spectra of CTS and its derivative (CTS GTFE) and b) H1 -NMR spectra of CTS derivative: (A) GTFE CTS), (B) CTS [17].

With GTFE CTS coating rendering limited results in terms of


barrier properties a different approach was considered in the
same work. Chemical grafting of the coated samples surface was
performed with poly(ethylene-alt-maleic anhydride) (PEMA) and
poly(maleic anhydride-alt-1-octadecene) (POMA), as displayed in
Scheme 1 [20]. The CTS-coated aluminum samples were
immersed, rst in a solution of glutaraldehyde to promote
cross-linking between CTS macromolecules and second in a
solution with PEMA or POMA. The reactions take place between
the functional groups of the glutaraldehyde (aldehyde moieties)
and the PEMA/POMA (maleic anhydride moieties) with the
primary amino groups of CTS. The structural difference between
PEMA and POMA is the existence of an additional aliphatic chain
in the case of POMA.

The modied CTS samples, besides the bands assigned to the


CTS polymeric chains, also display bands that can be ascribed1to
the structure of PEMA and POMA, namely at 2915 and 2850 cm ,
which demonstrates a successful modication of CTS surface
[20]. The interfacial properties of CTS-based coatings, namely
the hydrophobic character, were assessed by static water contact angle. Contact angles for CTS coatings were around 69 5
and slightly higher for CTS with 1/3 ethanol, around 73 5 .
The addition of MBT also increases the contact angles of CTS
to values around 78 6 . PEMA and POMA modied CTS coatings exhibit considerable higher values than CTS coatings, around
98 2 and 105 3 for CTS PEMA and CTS POMA, respectively.
In these cases, and as observed for unmodied CTS coatings, the

10

ox

R / cm

10

10

0.01

CTS
CTS_Ce_1 wt %
CTS_Ce_10 wt%

0.1

10

Time/days
Fig. 7. Effect of Ce3+ loading in the variation of oxide resistance of AA2024 coated
with CTS.

addition of MBT drastically increases the contact angles.


The addition of 10 wt.% MBT the contact angles
increase to 137 3 in the
case of CTS PEMA MBT and to 141 6 for samples grafted with
CTS POMA MBT.
For systems modied with PEMA/POMA the EIS spectra show
signicant differences when compared to unmodied CTS. In
both

Fig. 8. Release proles of MBT from CTS MBT in different conditions [19].
Reproduced with permission from ECS Electrochem. Lett. 2, Chitosan as a Smart
Coat- ing for Controlled Release of Corrosion Inhibitor 2-Mercaptobenzothiazole
(2013). Copyright 2013, The Electrochemical Society.

modied systems only one time constant ascribed to the oxide


response is detected. Furthermore, an interesting feature occurs
for CTS PEMA at high frequencies: in spite of the lack of detection
of a true time constant associated with coating response, the
solution

Fig. 9. EIS spectra acquired for AA2024 substrates coated with CTS lms loaded with MBT (1 wt.% and 10 wt.%) in 50 mM NaCl (a) and (b). In (c) are presented the
photographs of AA2024 plates coated with chitosan coatings after 25 min (A) and 1 week (B) of immersion in 50 mM NaCl solution. For (1) AA2024 coated with 5 layers of
CTS, (2) AA2024 coated with 5 layers of CTS 1 wt.% MBT, (3) AA2024 coated with 5 layers of CTS 10 wt.% MBT and (4) AA2024 coated with 5 layers of GTFE CTS 10 wt.% MBT
[20].

delays the ingress of electrolyte [20]. Nevertheless, the resistance


associated with this high-frequency time constant falls steeply
with immersion time. For longer immersion times the best system becomes CTS MBT, thereby emphasizing the short-term effect
provided by the interfacial modication of CTS.

2.5. Chitosan: a suitable coating for corrosion protection?

Scheme 1. Strategy for improvement of CTS barrier properties: functionalization


of bulk CTS matrix and hydrophobization of coating/solution interface [20].

resistance is higher than for CTS POMA and CTS. This effect could
be associated with the electrolyte resistance in the pores of the
coating, caused by the hydrophobization of the interface.
The coating modication with PEMA and POMA, in spite of
pro- viding good electrochemical performances
for
short
immersion times, rapidly disappears, an indication that the
hydrophobization of the interface only is not sufcient to provide
barrier effect under full immersion conditions.
Fig. 10 presents the EIS analysis of CTS PEMA and CTS POMA
coatings loaded with MBT, and shows that for early stages of
immersion all the three systems provide protection to the
substrate (CTS and CTS modied with PEMA or POMA) as
inferred from the similar responses at intermediate and low
frequencies. However, a relaxation process is detected at high
frequencies for the rst time for CTS systems studied [20], which
can be assigned the coating response/barrier effect in the
particular case of CTS POMA MBT. This behavior was explained
by combination of a hydrophobic effect of the modied surface
and the hydrophobicity of MBT that

In the previous sections data showed that chitosan can be


used as a polymer reservoir for different corrosion inhibitors
and its matrix is versatile enough to impart modications either
in the bulk or interface.
Clearly, the downside is the low barrier properties that the
unmodied, self-standing chitosan polymer confers. For highperformance applications in where the aluminum alloy 2024 is
used (e.g. aerospace structures), the developments achieved so
far with chitosan-based polymers are still in their infancy and
quite behind the required level of protection. From the around
150 scientic documents that can be found on this topic, only a
few are dedicated to protective coatings for aluminum substrates.
Therefore, there is still space for signicant developments in this
eld.
Some recent works have reported the preparation of composite coatings with chitosan to obtain protective systems to metal
substrates [28,29]. Indeed, the preparation of composites seems a
reliable way of obtaining coatings with the best of chitosan properties, namely the low toxicity and controlled release of active
species, combined with good mechanical properties rendered by
other components.
Another important aspect to consider is adhesion. In our work
described in Ref. [18]
adhesion failure was not observed
between chitosan and the top layer used (hybrid solgel), but this
parameter was not considered in detail. One may anticipate that
the easiness in functionalizing chitosan provides the right tools
to tune and improve adhesion to the metal as shown in the
work of Sugama [21]. At the same time chitosan can be modied
with substituents that are relevant to establish covalent bonds
with organic coat- ing layers such as epoxy- and isocyanatederivatives, among others [3032].
Another possibility is to use CTS in less demanding applications,
such as temporary protective coatings. For this type of applications
other parameters come into play, namely the possibility to remove
the coating only by washing the surface with mild acidic
solutions, allowing the recycling of CTS, the antibacterial
properties of CTS that limit the deposition of biolms and the low
price due to large availability of CTS.

Fig. 10. EIS spectra acquired for AA2024 substrates coated with CTS modied with PEMA and POMA and loaded with 10 wt.% MBT in 50 mM NaCl (a) and (b) [20].

3. Conclusions and future perspectives


In this review, the ability of CTS to function as a reservoir
for active species for corrosion protection was demonstrated. The
capacity of CTS to form good lms and the reversibility of
charging CTS amine groups provides foundations for further
development of active/smart coatings based on chitosan, and
extend the applica- tion of this polymer to other active metal
substrates.
More specically, the active protection provided by different
corrosion inhibitors was proved, the release of corrosion inhibitor
rationalized in terms of pH changes together with reversibility
of interactions between CTS polymeric chains. Nevertheless, the
active corrosion protection provided by CTS coatings seems more
appropriate for temporary protection, when applied alone or as
part of a multilayer coating system, working as a reservoir for the
corrosion inhibitor. The main challenge for use of CTS in high
perfor- mance applications is to drastically improve its barrier
properties.
Acknowledgements
This work was developed in the scope of the project CICECOAveiro Institute of Materials (Ref. FCT UID /CTM /50011/2013),
nanced by national funds through the FCT/MEC and when
applicable co-nanced by FEDER under the PT2020 Partnership
Agreement. JT thanks FCT for Researcher (IF/00347/2013) grant.
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