Progress in Organic Coatings 143 (2020) 105631

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Characterization of the chitosan-tungsten composite coating obtained by T

electrophoretic deposition
José Anderson Machado Oliveiraa,*, Renato Alexandre Costa de Santanab,
Alcides de Oliveira Wanderley Netoa,*
a
Institute of Chemistry, Federal University of Rio Grande do Norte, 59078-970, Natal, RN, Brazil
b
Health and Education Center, Federal University of Campina Grande, 58175-000, Cuité, PB, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: In this research, a new type of composite coating made of chitosan-tungsten (Chit-W), was obtained by the
Electrodeposition process of electrophoretic deposition (EPD) and characterized. The deposition parameters (potential and pH)
Chitosan were evaluated. The results of surface morphology (SEM), chemical composition (EDS), crystallography (XRD)
Tungsten and infrared spectroscopy (FT-IR) confirmed the deposition of the composite film consisting of a tungsten im-
Corrosion
pregnated chitosan matrix with different morphology types. Corrosion resistance results obtained by potentio-
dynamic polarization (PP) and electrochemical impedance spectroscopy (EIS) showed that the coatings can be
applied for temporary protection of exposed steel (1020) in NaCl (3.5 %) medium. Therefore, this work proves
the deposition of a new class of chitosan-based composite materials with potential applications in different
technological sectors.

1. Introduction applicability to different metals and iron-based alloys [13]. Due to

Chitosan is a naturally occurring biopolymer, it can be obtained as a
product of the alkaline deacetylation reaction of chitin, which is a
polysaccharide found in crustacean shells, fungal cell walls and insect
cuticles [1,2]. Due to its properties such as biocompatibility, anti-
bacterial activity, non-toxicity, biodegradability and the ability to form
good films, chitosan has aroused the interest of scientific community in
recent years [3,4]. Thus, chitosan-based coatings can be applied in
different sectors, such as the production of biomedical materials, bio-
sensors, the food industry, the textile and cosmetics industry, amongst
other applications [5,6].
Electrophoretic deposition (EPD) is the most widely used technique
for producing chitosan coatings [7,8], since it allows the control of
deposition parameters to obtain films with specific properties on sub-
strates with complex geometries, besides the possibility of obtaining
coatings at room temperature [1,9,10].
Using corrosion inhibitors to protect metallic materials exposed to
harsh environments is a common practice in many industrial sectors
[2,11,12]. Anodic inhibitors, which act to inhibit anodic reactions, are
used for the purpose of producing a passivation layer on the material to
be protected. Chromate (CrO42−) stands out as an anodic inhibitor for
its excellent corrosion protection properties, as well as its wide
structural and electronic similarity, other ions such as Tungstate
(WO42−) and Molybdate (MoO42−) are also widely used for anodic
protection of metallic materials [14].
Fakhri et al. [15] evaluated the photocatalytic performance of WS2
particles immobilized on chitosan in the degradation of Neomycin as an
aminoglycoside antibiotic. The authors confirmed the degradation of
Neomycin using WS2/Chitosan nanofibers and UV light irradiation.
Wang et al. [16] used chitosan and polyoxometalates as precursors in
the fabrication of a tungsten oxide composite supported by a meso-
porous carbon matrix doped with nitrogen. The authors concluded that
WO3-x-based composite materials can be applied in the catalytic re-
duction of organic pollutants induced by oxygen vacancy and infrared
radiation-driven H2 production. Firouzi et al. [17] studied the effect of
chitosan-coated tungsten trioxide nanoparticles as a contrast agent for
X-ray computed tomography. The results showed that chitosan coated
WO3 nanoparticles can attenuate X-rays more efficiently than a com-
mercially available iodinated contrast agent at the same concentrations.
For a better approach to the electrophoretic deposition of chitosan-
based composite materials applied in the biomedical area, consult the
paper recently published by Avcu et al. [18].
To the best of our knowledge, this is the first investigation on the
electrophoretic deposition of a chitosan-tungsten (Chit-W) composite

⁎
Corresponding authors.
E-mail addresses: jmo.anderson@gmail.com (J.A.M. Oliveira), alcideswanderley@hotmail.com (A.d.O. Wanderley Neto).

https://doi.org/10.1016/j.porgcoat.2020.105631
Received 14 November 2019; Received in revised form 29 February 2020; Accepted 29 February 2020
0300-9440/ © 2020 Elsevier B.V. All rights reserved.
J.A.M. Oliveira, et al.
film, using sodium tungstate as tungsten source. The coatings obtained
were characterized by scanning electron microscopy (SEM), chemical
composition (EDS), X-ray diffraction (XRD), and Fourier transform in-
frared spectroscopy (FT-IR). Its corrosion resistance in NaCl (3.5 %) was
evaluated by potentiodynamic polarization (PP), and electrochemical
impedance spectroscopy (EIS). Therefore, the goal of this work was to
investigate the deposition parameters (potential and pH) for obtaining a
new composite coating of Chit-W, with potential application in dif-
ferent technological and industrial sectors.
2. Material and methods
2.1. Materials
Chitosan of medium molecular weight (approximately 85 % dea-
cetylated) was purchased from Polymar LTDA (Brazil), glacial acetic
acid (CH3COOH) from Isofar LTDA (Brazil), sodium tungstate
(Na2WO4•2H2O) and sodium hydroxide (NaOH) from Neon comercial
(Brazil), were used as received on the preparation of the electrolytic
suspension. The reagents were dissolved in deionized water.
2.2. Electrophoretic deposition
Chitosan (0.5 g/L) was dissolved into an aqueous solution of acetic
acid (1% vol.) with magnetic stirring for 24 h at room temperature
(25 ± 2 °C). Sodium tungstate (1 mM) was added to the chitosan so-
lution under magnetic stirring over a period of 1 h. The suspension pH
(3.5 and 5.5) was adjusted with NaOH (1 M). Deposition was carried
out at 25 ± 2 °C, over 10 min at potentials of 5 and 10 V, utilizing
80 mL of electrolyte suspension.
Carbon steel (1020) plates (30 mm x 15 mm x 1 mm) were used as
cathode and stainless steel (316 L) plates (50 mm x 20 mm x 1 mm) as
anode. The distance between the electrodes was 15 mm. The carbon
steel (1020) plates were polished mechanically with SiC sandpapers of
300, 400, 600, and 1200 grit, until a polished mirrored surface was
obtained, after polishing, the electrodes (steel 1020) were washed with
acetone, ethanol and distilled water, separately, to remove residues left
after polishing, and immediately used for deposition. After deposition,
the coated plates were dried at a temperature below 50 °C and stored in
a desiccator for further analysis and characterization. Table 1 presents
an encoding for the composite films obtained in each experimental
condition.
2.3. Material characterization
The surface morphology of the films was evaluated by Scanning
Electron Microscopy (SEM, TESCAN VEGA 3SBH with dry EDS detector
from Oxford X-ACT IE150). To measure electrophoretic mobility (μE),
one was used Zeta-Meter System 3.0+ (Zeta Meter Inc., USA); mea-
surements were made in triplicate and at room temperature
(25 ± 2 °C). The zeta potential (ZP) was calculated from the μE value
using the Smoluchowski relationship [19]. The films were characterized
by Fourier-transform Infrared Spectroscopy (FT-IR) at the wave number
of 4000−500 cm−1 (BIO RAD EXCALIBUR FTS 3000MX), before ana-
lysis the films were scraped from the electrode right after the deposition
process, still moist to facilitate their removal from the substrate (1020
Table 1
Codification of composite films and operational deposition conditions.
Composite coating Potential (V) pH Deposition time (min.)
Chit-W1 10 5.5 10
Chit-W2 10 3.5 10
Chit-W3 5 5.5 10
Chit-W4 5 3.5 10
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Progress in Organic Coatings 143 (2020) 105631
steel), and stored in a desiccator to remove moisture before FT-IR
analysis. The characterization of the physical microstructure of the
composite coatings was carried out by X-ray Diffraction, using a SHI-
MADZU diffractometer (model XRD-6100) with Cu Kα (λ =1.54056 Å)
radiation at 30 KV and 30 mA.
2.4. Electrochemical characterization
Corrosion resistance was evaluated using the Potentiodynamic
Polarization (PP) and Electrochemical Impedance Spectroscopy (EIS)
techniques, the measurements were conducted with a potentiostat/
galvanostat (PG STATE 30 from AUTOLAB) connected to the software
NOVA version 1.11 for data analysis. The tests were carried out in a
conventional electrochemical system with three electrodes, with a sa-
turated calomel electrode (SCE) as a reference, a platinum wire was
used as a counter electrode and a steel (1020) with and without the
Chit-W composite coatings were used as the working electrodes, pre-
senting a surface area of 0.76 cm² exposed to the corrosive medium for
analysis.
The scanning range for obtaining the PP curves was ± 0.3 V (vs
SCE) from the open circuit potential (OCP) at a scan rate of 1 mV/s. The
OCP was stabilized for 30 min before the PP measurements. The EIS
experiments were performed on the open circuit potential with a fre-
quency range of the order of 100 kHz to 10 mHz with an amplitude
signal of 0.01 V, in the first 24 h of exposure to the test solution. The
corrosive medium used in corrosion testing was NaCl (3.5 %), aiming to
simulate a marine environment for application in industrial sectors at
room temperature (25 ± 2 °C). All experiments were carried out in
triplicate to confirm the reproducibility of the results.
3. Results and discussion
Fig. 1 shows the SEM images and the cross section of the Chit-W
coatings. Different morphologies were obtained depending on the op-
erational conditionals used in the deposition of the films. The coating
Chit-W1, obtained at 10 V and pH 5.5 (Fig. 1a), shows microparticles on
its surface. Moreover, it is not possible to observe defects on the coat-
ings that can reach the substrate (cross section, Fig. 1b). In contrast, the
coating Chit-W2, obtained at 10 V and pH 3.5 (Fig. 1c), shows micro-
fractures that can reach the substrate. It is also possible to observe in
the cross section image (Fig. 1d) that this coating does not present good
adhesion to the substrate. Coatings obtained at 5 V (Chit-W3 and Chit-
W4) showed totally distinct morphologies depending on the electrolytic
suspension pH. In the film obtained at pH 5.5 (Chit-W3; Fig. 1e), the
non-homogeneous deposition of the composite film was observed, as it
can be better seen at the cross section image (Fig. 1f). In contrast, the
film obtained at pH 3.5 (Chit-W4; Fig. 1g) showed a more homogeneous
surface, despite the presence of defects that can reach the substrate
(Fig. 1h).
These observations prove the significant influence of the pH of the
electrolytic suspension used in the deposition of composite films of
chitosan. Similar results to that found in this work, for the morpholo-
gical characteristics of chitosan-based composite films were observed in
literature for the zinc-chitosan oxide composite coating [20], for the
chitosan/gelatin/bioglass composite [9], and for the MnO2-chitosan
nanocomposite [21].
Table 2 presents the values of coating thickness, measured at dif-
ferent points (in triplicate) from the SEM images of the cross section of
the coatings and the results of zeta potential (ZP) of the suspension used
for deposition.
The pH of the electrolyte suspension directly affects the zeta po-
tential value. According to literature, particles that have high values of
zeta potential have greater mobility and, therefore, move more quickly
towards electrodes with opposite charge, thus, a higher deposition rate
can be achieved by increasing the zeta potential and decreasing the
suspension viscosity [22,23].
J.A.M. Oliveira, et al. Progress in Organic Coatings 143 (2020) 105631

Fig. 1. SEM: a, b) Chit-W1; c, d) Chit-W2; e, f) Chit-W3; g, h) Chit-W4.

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J.A.M. Oliveira, et al.
Table 2
Values of thickness of the Chit-W coatings and zeta potential (ZP) of the elec-
trolytic suspension.
Experiment Thickness (μm) pH (suspension) ZP (mV)
Chit-W1 3.9 ± 0.8 5.5 45.6 ± 2.0
Chit-W2 3.3 ± 1.3 3.5 25.8 ± 1.9
Chit-W3 2.3 ± 0.5 5.5 45.6 ± 2.0
Chit-W4 3.8 ± 0.3 3.5 25.8 ± 1.9
The results of zeta potential (Table 2) showed positive values for the
two pH values of the electrolyte suspension. Therefore, deposition of
the Chit-W composite is cathodic, since, in addition to a measure of the
stability of the suspension, the value of the zeta potential also indicates
the direction of movement of particles charged in solution [1,24]. The
positively charged chitosan molecules in an acidic medium favor the
increase of the zeta potential value of the suspension [18,25]. Ac-
cording to Avcu et al. [18] suspensions with zeta potential values
greater than approximately 30 mV can generally be considered stable.
It is observed that the values of layer thickness varied in the range of
2.3–3.9 μm (Table 2), depending on the potential and pH values of the
suspension used, since the deposition time was the same for all ex-
periments (10 min). A linear relationship between the deposited mass
and the deposition time is generally accepted in literature, under con-
stant conditions of potential, pH and concentration of the reactant
species [26,27]. In addition, a linear relationship between the deposited
mass and the applied potential can also be observed; however, higher
potential values can generate non-homogeneous coatings and decrease
the rate of deposition [27,28]. Also according to literature, pH plays an
important role in the stability of electrolyte suspension and in charge
density of particles used in the deposition process, also influencing the
rate of electrophoretic deposition [28]. Thus, when the time is kept
constant, other parameters, such as potential and pH of suspension can
directly influence the rate of deposition and the morphological char-
acteristics of the coatings obtained by EPD [26–28].
Fig. 2 shows the chemical composition results obtained by EDS (EDS
maps for tungsten: W). A homogeneous distribution of tungsten on the
surface of all coatings can be observed (EDS maps, Fig. 2a, b, c, and d).
EDS spectra also show the presence of carbon and oxygen that can be
associated with the deposited chitosan matrix [23,29].
Cheng et al. [30], in a study about the process visualization of
electrophoretic deposition of chitosan hydrogels, identified a transition
region of sol-gel on the electrode interface as a function of the pH
gradient established between electrolytic suspension and the region
near the electrode due to electrochemical reactions. According to Bat-
manghelich and Ghorbani [31], deposition of colloid particles can be
controlled by diffusion when electrolytic suspension with elevated pH
are used; moreover, according to the authors, pH of electrolytic sus-
pension might influence the neutralization degree of the deposited
polymer, so cathodic deposits show an increase in the degree of neu-
tralization when pH of suspension is reduced. Therefore, by directly
having influence on the deposition mechanism, the characteristics of
chitosan coatings obtained at different values of pH might present
significant differences, as observed in our research for the surface
morphology results (Fig. 1).
Cathodic neutralization mechanism is the most accepted pathway
for chitosan films electrophoretic deposition (Eqs. 1–3). The chitosan
molecules become positively charged in an acidic medium (pH < 6.5),
through the protonation of amine groups. Due to electrostatic attrac-
tion, the chitosan molecules move to the surface of the cathode and
deposit in the shape of an insoluble film through the neutralization of
amine groups by hydroxide ions generated on the surface of the cathode
[26,32,33].
Chitosan-NH2 + H3O+ → Chitosan-NH3+ + H2O (1)
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Progress in Organic Coatings 143 (2020) 105631
2H2O + 2e− → H2 + 2OH− (2)
−
Chitosan-NH3+ + OH → Chitosan-NH2 + H2O (3)
The evolution of hydrogen on the surface of the cathode during the
deposition process (Eq. 2) can generate defects in its morphological
structure [9,34]. Gebhardt et al. [4] showed the significant influence of
the electric field used on the deposition process on the surface mor-
phology results and thickness of chitosan coatings. The authors con-
cluded that, using elevated electric fields (up to 10 V/cm), thicker
coatings can be obtained, however increasing the potential can con-
tribute for an elevation in the quantity of bubbles produced in the de-
position process, which causes a negative influence on the quality of the
obtained coatings. Thus, this influence of potential allied to modifica-
tions on the deposition mechanism caused by pH variations of the
suspension can explain the morphological characteristics observed in
this work.
The influence of the evolution of hydrogen gas on the cathode
surface during the deposition process (Eq. 2) is noted, because at the
lowest pH (3.5) there is a higher concentration of H+ ions and, there-
fore, a high potential will increase the amount of gas formed on the
cathode surface, thus hampering regular deposition process of the
composite film. In conditions of higher pH (5.5) the evolution of hy-
drogen gas is less, therefore, a greater potential will increase the elec-
trophoretic mobility of positively charged chitosan molecules and,
therefore, increase the concentration of chitosan on the cathode sur-
face, favoring the deposition of a more homogeneous film under these
conditions [28,33]. In addition, the greater stability of the suspension at
pH 5.5, evidenced by the higher zeta potential value (45.6 mV;
Table 2), can also influence the deposition process and favor formation
of more homogeneous coatings [18]. Fig. 3 shows the FT-IR spectra of
the composite coatings and of chitosan as received (chitosan powder),
used for comparison.
The chitosan spectrum (Fig. 3e) shows specific signals, with em-
phasis on the peaks around 896 cm−1 and 1151 cm−1 that are attrib-
uted to the vibrations of the glycosidic bonds of the saccharide structure
(eCeOeCe) [4,11]. The peaks at 2871 cm−1 and 2919 cm−1 are at-
tributed to the CeH vibration; peaks at 1035 cm−1 and 1062 cm−1 are
attributed to the CeO stretching vibration [4,35,36]. The peaks located
at 1376 cm−1 and 1413 cm−1 are attributed to the symmetric de-
formation modes of the CH3 group [4,35]. The peak at 1318 cm−1 can
be attributed to the deformation vibration of the CeH group linked to
the NeH group (amide III) [4,37]. The peak at 1580 cm−1 was attrib-
uted to the NeH bending of the amine group; the peak at 1656 cm−1
was attributed to the stretching vibration C]O of the amide group I
[4,35]. The broad band located between 3357 to 3440 cm−1 is attrib-
uted to the stretching vibration of −OH and NH [4,17,35]. The spectra
of the Chit-W coatings displayed similar results to that of chitosan, with
highlights to the coating Chit-W1 (Fig. 3a).
These results show that the Chit-W1 film, obtained under 10 V and
pH 5.5 operating conditions, was deposited under optimal conditions to
obtain a stable chitosan matrix. Dev et al. [28] in his study of electro-
phoretic chitosan deposition also found similar results. The authors
concluded that potentials greater than 10 V produce large amounts of
gas on the cathode surface, making the deposition process more diffi-
cult; at pH values below 5.5, decrease in the density of net charge of
chitosan can influence the rate of deposition and, consequently, the
adequate formation of chitosan coatings.
A decrease in the quantity and intensity of the peaks/bands for the
composite films in relation to the chitosan powder can be observed in
the FT-IR spectra (Fig. 3). This can be explained by the interaction
between chitosan functional groups and tungsten during formation of
the composite [21,38].
According to Hassan et al. [21], in their study about the synthesis of
the composite films of MnO2-chitosan, the film formation can be ex-
plained by different types of interactions, as, for instance, electrostatic
J.A.M. Oliveira, et al. Progress in Organic Coatings 143 (2020) 105631

Fig. 2. EDS: a) Chit-W1; b) Chit-W2; c) Chit-W3; d) Chit-W4.

5
J.A.M. Oliveira, et al.
Fig. 3. FT-IR: a) Chit-W1, b) Chit-W2, c) Chit-W3, d) Chit-W4, e) Chitosan
powder.
Fig. 4. XRD parameters: a) Steel (1020), b) Chit-W1, c) Chit-W2, d) Chit-W3, e)
Chit-W4.
interactions, weak interactions of Van der Walls, and hydrogen bonds
between the nanoparticles of MnO2 and hydroxyl groups and primary
amines present in the polymeric chain of chitosan. Tabesh et al. [29]
attributed the formation of chitosan-copper composite film to the
changes in intensity and displacement of infrared signals associated to
NeH groups, possibly due to interactions between these groups and
copper nanoparticles. Vold et al. [39] in their study on the selectivity of
ion binding to chitosan concluded that the formation of complexes
between chitosan and metal ions increases with increasing pH, in-
dicating an interaction between metal ions and chitosan deprotonated
amino groups. Therefore, changes observed in the intensity and posi-
tion of the diffraction peaks associated to functional groups amino of
chitosan can be indicative of its interaction with tungsten for the for-
mation of the Chit-W composite. The XRD results are presented in
Fig. 4.
The diffraction parameters of the composite Chit-W1 shows
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Progress in Organic Coatings 143 (2020) 105631
characteristic signs of semi-crystalline chitosan at 2θ = 9-10° and
2θ = 19-20° [29,40]. In turn, the composites Chit-W2 and Chit-W4 only
showed the peak at around 2θ = 9-10°. These results confirm the de-
position of the chitosan film on the steel substrate. In the composite
Chit-W3 only the substrate peaks (1020 steel) at approximately
2θ = 45° (110) and 2θ = 65° (200) are displayed (ICDD file 01-087-
0721) [41].
The absence of chitosan peaks in the composite film obtained at 5 V
and pH 5.5 operating conditions (Chit-W3) can be attributed to the
deposition of a thin, non-homogeneous and amorphous coating on the
electrode surface. Similar results were found in literature for hydro-
xyapatite-silver-chitosan nanocomposite obtained by electrodeposition
[42], for a chitosan-graphene nanocomposite [43], and in a study on
the chitosan-mediated electrosynthesis of organic-inorganic nano-
composites [33]. Thus, a better characterization of Chit-W3 film was
realized by the results of SEM, EDS and FT-IR.
The absence of the peak at 2θ = 19-20° in the films obtained at pH
3.5 (Chit-W2 and Chit-W4) can be attributed to the use of a less stable
electrolyte suspension for deposition of these films, based on the lower
zeta potential value of the suspension (ZP =25.8 mV) at this pH value
(Table 2), thus leading to the deposition of less stable and more
amorphous chitosan matrices compared to Chit-W1 film that was ob-
tained from a more stable suspension (ZP =45.6 mV; Table 2)
[1,18,22]. In addition, the use of a more suitable potential for deposi-
tion of more homogeneous chitosan films may explain the differences
observed in the XRD results between the composite films Chit-W1 and
Chit-W3, since both were obtained using suspensions with the same
value of pH [28].
Literature reports that hydrogen bonds between the amino and
hydroxyl groups of chitosan can be broken due to the interaction of
chitosan molecules with other species in the formation of complexes,
thus leading to a decrease in the degree of crystallinity of chitosan films
obtained by electrophoretic deposition [32,40,42,43]. Francis et al.
[44] attributed the absence of chitosan peaks to a smaller degree of
crystallinity after conversion of the coating with magnesium, because,
according to the authors, there is a direct relationship between chitosan
films crystallinity and the degree of deacetylation of the polymer.
Moreover, broadening of the diffraction peaks indicates a decrease in
the crystallinity of chitosan films [40]. Therefore, interaction between
chitosan molecules and tungstate ions, combined with the influence of
operational conditions used for deposition of composite films, may
explain the results of XRD observed. The absence of tungsten peaks can
be explained by the small amount of salt used to prepare the stable
suspension for the deposition process. Fig. 5 shows a possible me-
chanism for depositing the composite film Chit-W.
Composite coatings with chitosan can be obtained due to its capa-
city to form hydrogen bonding between the amine or hydroxide groups
present in its polymeric structure with other organic molecules, or by
chelation with inorganic species (metallic ions, for instance) [39].
Furthermore, according to Rinaudo [45], chitosan can form an elec-
trostatic complex in acidic environment, thus, owing to the charge ac-
quired by chitosan molecules in acidic solutions (pH < 6.5), electro-
static interactions between the cationic polyelectrolyte and negatively
charged species are also possible [1,20]. Hence, the electrostatic at-
traction mechanisms between positively charged chitosan molecules
and negatively charged tungstate ions (WO42−), in addition to chit-
osan’s ability to form complexes with metallic ions, can explain the
formation of the Chit-W composite film.
The mechanism proposed to explain electrophoretic deposition of
the composite film Chit-W is based on electrostatic interaction between
the positively charged chitosan molecules and the negatively charged
tungstate ions, combined with chitosan chelation capacity [1,39]. Si-
milar mechanisms have been proposed in literature to explain the for-
mation of chitosan-based composite films with inorganic species, such
as, for example, gold nanoparticles [46], bioglass [7,47], hydro-
xyapatite [18,47], silver nanoparticles [48], and zinc oxide [20].
J.A.M. Oliveira, et al. Progress in Organic Coatings 143 (2020) 105631

Fig. 5. Illustration of the Chit-W composite film deposition mechanism.

Table 3 A shift towards more noble values of the corrosion potential (Ecorr)
Electrochemical results of corrosion in NaCl (3.5 %), at 25 ± 2 °C. in the composite coatings can be observed in the PP curves in com-
Experiment Ecorr (V) icorr (μA/cm²)
parison to uncoated 1020 steel. The corrosion current density (icorr) of
the Chit-W1 composite film has shown that this coating has a better
Steel (1020) −0.75 ± 0.02 6.0 ± 1.7 corrosion resistance performance compared to uncoated commercial
Chit-W1 −0.64 ± 0.08 4.0 ± 0.2 steel (1020) and other composite films (Table 3). SEM results (Fig. 1a,
Chit-W2 −0.69 ± 0.01 6.6 ± 0.4
Chit-W3 −0.64 ± 0.08 5.0 ± 2.1
b), FT-IR (Fig. 3a) and XRD (Fig. 4b) showed that this coating is con-
Chit-W4 −0.65 ± 0.03 7.7 ± 1.6 stituted by a well-formed and uniform chitosan matrix, with a homo-
geneous distribution of tungsten (Fig. 2a), which does not have defects
in its surface structure, acting as a more efficient protective barrier
between the corrosive medium and the substrate (1020 steel), in
comparison with other composite coatings, thus reducing the diffusion
of corrosive species on the steel surface [51]. It should be noted that in
aerated solutions, the cathodic current density in the plateau can be
related to the corrosion current of the materials exposed in neutral
solutions, therefore, the cathodic current density in the plateau can also
be an indication of the icorr value of the materials investigated here
[52].
It can be seen in the polarization curves that the cathodic and
anodic reaction were affected by the obtained coatings. Similar result
was observed in the literature [36]. As described by Pozo et al. [53] the
corrosion potential shift towards less negative values allied to a re-
duction of the corrosion current density might indicate a decrease in the
Fig. 6. Polarization curves ( ± 0.3 V vs OCP), in NaCl (3.5 %). thermodynamic and kinetic tendency of the corrosive process. In ad-
dition, modifications in the anode and cathode branch shapes of the
Therefore, when the chitosan molecules are attracted to the cathode polarization curves promote modifications in the metal dissolution
(electrophoresis) they drag the tungstate ions with them, forming a process under corrosive conditions.
chitosan matrix impregnated with tungsten after the cathodic neu- According to Pitakchatwong et al. [54] an organic corrosion in-
tralization of chitosan molecules (Eq. 3). hibitor can be classified as anodic or cathodic when the change of
According to Tsyntsaru et al. [49] the electrodeposition of metallic corrosion potential is more than 85 mV. The authors observed that the
tungsten from aqueous solution is not possible due to the formation of inhibition system investigated did not present changes greater than
tungsten oxide on the cathode surface. Therefore, tungsten oxide may 85 mV, so they classified their material as a mixed inhibition system.
also be formed electrochemically on the cathode surface along with the Therefore, by presenting a potential corrosion change less than 85 mV,
electrophoretic deposition of chitosan simultaneously. A similar result allied to the presence of impregnated tungsten in the chitosan matrix,
was observed for the formation of the MnO2-chitosan composite [21]. the Chit-W coating investigated in this research can also be considered
The FTIR, XRD results together with the SEM/EDS images provide as a mixed protection system (anodic/cathodic).
prove for the formation of the Chit-W composite film. The significant influence of electrolytic suspension pH can high-
Table 3 presents the results of the corrosion parameters, such as lighted, because best corrosion resistance results were observed when
corrosion potential (Ecorr) and corrosion current density (icorr) obtained pH was evaluated at the highest value, pH 5.5 (Table 3). Batmanghelich
by Tafel, using the Tafel’s extrapolation technique of straight lines in and Ghorbanin [31] found similar results in research study about the
the potentiodynamic polarization (PP) curves of 1020 steel coated with corrosion resistance of chitosan-hydroxyapatite-carbon nanotube com-
Chit-W composites and without coating (Fig. 6) [13,50]. posite. The authors observed an increase in the corrosion resistance of
the composite with increase in pH of the suspension. They attributed

7
J.A.M. Oliveira, et al.
Fig. 7. Impedance spectra (Nyquist plots), obtained at different times of im-
mersion in NaCl (3.5 %): a) Steel (1020), b) Chitosan (EPD), c) Chit-W1.
this result due to decrease in degree of neutralization of the polyelec-
trolyte in conditions of elevated pH (pH around 5), because this causes
a size increase in the structural units of the polyelectrolyte leading to a
decrease in the suspension stability and, consequently, the deposition
process is facilitated generating thicker coatings. It also enables better
structure, ensuring better barrier properties, in comparison to the
coatings obtained from suspensions with low pH (pH around 3). This
phenomenon was also observed in this work.
EIS experiments were carried out for the best corrosion resistant
coating (Chit-W1) and also for 1020 steel without coating and for a
chitosan film without tungsten deposited under the same conditions as
the composite film Chit-W1 (10 V; pH 5.5), used for comparison. The
EIS diagrams obtained for different NaCl immersion intervals (3.5 %),
at room temperature (25 ± 2 °C), are shown in Fig. 7.
The formation of a single semicircle in the region of high fre-
quencies was observed in the impedance diagrams, corresponding to a
load transfer resistance process. It is also possible to observe the pos-
sibility of formation of a second phenomenon in the low frequency
region after 24 h of exposure to the corrosive medium for all the three
systems, probably caused by diffusion processes of electrochemically
active species on the surface of the electrodes [43,55]. It was observed
that after 24 h of immersion, the steel significantly decreased its re-
sistance to corrosion in comparison to the other systems (Fig. 7a–c).
Furthermore, impedance diagrams are not perfect semicircles (de-
pressed semicircle), which may indicate a porous and inhomogeneous
surface for the three systems [7,13,21,56].
The three systems studied presented similar behaviors during the
immersion period, that is, an increase in the impedance values up to 2 h
8
Progress in Organic Coatings 143 (2020) 105631
after immersion, followed by a reduction in the impedance value up to
24 h after immersion. Although the impedance values are similar to the
three systems tested, it was observed that the composite film Chit-W1
showed higher impedance values in almost all the immersion periods
evaluated in general.
The highest value of charge transfer resistance (Ret), which can be
obtained by the semicircle diameter of the impedance diagram [7,43],
was exhibited by the film Chit-W1 (Fig. 7c) reaching approximately 4.5
KΩ cm², followed by the pure chitosan film with 3.4 KΩ cm² (Fig. 7b)
and uncoated 1020 steel with 2.9 KΩ cm² (Fig. 7a), all after 2 h of
immersion. These results show that the addition of tungsten can in-
crease the corrosion resistance of pure chitosan films; also, the com-
posite film can decrease the ion diffusion process and, thus, reduce the
rate of corrosion in the substrate (1020 steel). Therefore, despite having
a limited barrier effect, the Chit-W composite film can decrease the
active area on the surface of 1020 steel. Similar results have been ob-
served in literature, whereby the addition of an inorganic species to the
chitosan matrix increased corrosion resistance of the composite coating
[7,29,42,46].
Therefore, increase in corrosion resistance of the composite coating
can be attributed to the ability of chitosan to form a protective barrier
between the substrate and the corrosive medium, coupled with the
presence of tungsten and the possible formation of a passive layer of
WO3 [36,57]. According to Sambyal et al. [13], coatings applied on
metallic surfaces showed accelerated corrosion when exposed to a
medium containing chloride ions (Cl−), due to their high rate of dif-
fusion. Thus, to assure an efficient protection against corrosion, the
coatings must present structural integrity associated with the recovery
capacity of the possible damages caused by the corrosion process.
These results show that Chit-W composite coatings can be applied in
the protection of 1020 steel in NaCl (3.5 %) medium, mainly in tem-
porary protection applications during the storage or transportation of
metallic structures, as it is observed that there was no significant im-
provement in the corrosion resistance of 1020 steel for long-term ap-
plications. These results can be explained by the porous nature usually
presented by chitosan coatings obtained in aqueous suspensions due to
the intense evolution of hydrogen gas on the cathode surface [7,56].
Therefore, future investigations will focus on the use of other solvents
to decrease the amount of hydrogen gas formed during the EPD process
and, thus, deposit better coatings with less porosity, in order to increase
the corrosion resistance of the material for more prolonged applica-
tions; in addition to investigating a possible application of the compo-
site film Chit-W as a surface coating for metal implants used in ortho-
pedic surgeries.
4. Conclusion
Chitosan-tungsten (Chit-W) composite coatings were successfully
obtained by electrophoretic deposition (EPD). The composite films
obtained are formed by a chitosan matrix impregnated with tungsten
and presented different morphological and structural characteristics
depending on the values of the parameters, potential and pH of the
electrolytic suspension, used in the deposition process.
Corrosion resistance results showed that Chit-W films can be applied
as temporary coatings to protect 1020 steel in corrosive NaCl (3.5 %)
medium because, due to its film-forming properties, chitosan has the
necessary characteristics for applications such as protective coatings or
corrosion inhibitors where film removal is required prior to using the
materials [58]. The composite film obtained in operation conditions of
10 V and pH 5.5 (Chit-W1) showed the highest resistance to corrosion
amongst the composite coatings evaluated. Therefore, this work paves a
way to obtain a new class of chitosan-based materials via electro-
phoretic deposition.
J.A.M. Oliveira, et al.
CRediT authorship contribution statement
José Anderson Machado Oliveira: Methodology, Investigation,
Writing - original draft, Visualization. Renato Alexandre Costa de
Santana: Validation, Resources, Writing - review & editing. Alcides de
Oliveira Wanderley Neto: Conceptualization, Writing - review &
editing, Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) -
Finance Code 001.
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