Surface & Coatings Technology 369 (2019) 311–322

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Surface & Coatings Technology

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

Effect of initial surface treatment on obtaining a superhydrophobic surface T

on 5052 aluminum alloy with enhanced anticorrosion properties
⁎
Rafael G.C. da Silvaa, Magda R.S. Vieiraa, , Maria I.C. Maltaa, Carlos H. da Silvaa,
Sara H. de Oliveirab, Severino L.U. Filhoa
a
Department of Mechanical Engineering, Federal University of Pernambuco, Recife 50740-550, Brazil
b
Department of Chemical Engineering, Federal University of Pernambuco, Recife 50740-590, Brazil

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

Keywords: Although there are many studies about superhydrophobicity on aluminum alloys substrates and their resistance
Aluminum alloy to corrosion, few studies have evaluated the effect of the initial surface condition on obtaining super-hydro-
Superhydrophobic surface phobic surfaces. Different initial surface treatment (sanded, blasted and untreated) conditions were investigated
Corrosion on 5052 aluminum alloy to evaluate their influence on obtaining superhydrophobic surfaces with anticorrosive
Surface treatment
properties in saline medium. These surfaces were obtained in three sequential steps: acid etching in hydrochloric
Roughness
acid solution; chemical treatment in zinc nitrate in alkaline medium; and finally, reducing surface energy by
using stearic acid. The characteristics of the surface were studied using scanning electron microscopy, energy
dispersive spectroscopy, confocal microscopy and contact angle measurements. The corrosion resistance was
evaluated by linear potentiodynamic polarization. The results revealed that the initial surface condition influ-
enced the superhydrophobic and anticorrosion properties of the coatings. The sample initially sanded presented
the best results of contact angle, sliding angle and efficiency of corrosion resistance, with values of 154°, 5.67°
and 89.82%, respectively. However, after immersion corrosion test for 28 days, the coating lost super-
hydrophobic character and presented hydrophilic behavior.

1. Introduction
The importance of aluminum and its alloys as engineering materials
are seen to have increased because they have been applied in a wide
range of industrial areas, such as aerospace, transportation, civilian and
shipping industries, due to their low cost, low density, excellent ma-
chinability, high fatigue strength and easy accessibility [1–4]. However,
halide ions, especially Cl−, dissolved in water, can penetrate the nat-
ural oxide layer of an aluminum alloy and destroy the passivity of the
material at localized points [5,6]. In the active-passive cell formed, the
anodic area is located at points where the passive layer is destroyed,
and these areas are very small compared to the cathodic areas. There-
fore, the corrosion process will be accelerated at these points [7].
Superhydrophobic (SHP) surfaces have been studied as an alter-
native to inhibiting corrosion as they reduce the contact between
aqueous electrolyte and the surface of the material, thereby preventing
the electrochemical corrosion process, since the electrolyte does not
reach the substrate. The development of super-hydrophobic surfaces in
aluminum, has been contributing to increase the use of this metal in
engineering fields, such as shipbuilding and oceanographic engineering
[8–10].
A surface can be characterized as superhydrophobic by the value of
the contact angle (CA). Contact angles smaller than 10° are a char-
acteristic of superhydrophilic surfaces. Hydrophilic surfaces present
contact angles smaller than 90°, unlike hydrophobic surfaces, the angles
of which have values of between 90° and 150°. When the contact angle
is higher than 150°, the surface is superhydrophobic (Fig. 1) [11,12].
The superhydrophobic phenomenon is inspired by the water re-
pellency that occurs on lotus leaves, butterfly wings, or shark skin and
is directly related to the concept of wettability. Empirical models were
proposed to relate wettability with the morphology of a surface. The
two most notable are the models of Wenzel and Cassie-Baxter, both of
which are used to study wettability on rough surfaces [13].
Wenzel considered a homogeneous interface between the droplet
and the rough surface, where the liquid fills the entire space of the
cavities of the roughness. According to the Wenzel model, as the
roughness increases on an initially hydrophobic surface, the hydro-
phobicity effect will also increase. However, for hydrophilic surfaces it
has the opposite effect, namely the contact angle decreases as the
roughness increases [14,15].

⁎
Corresponding author at: Department of Mechanical Engineering, Federal University of Pernambuco, Av. da Arquitetura, s/n°, 50740-550 Recife, Brasil.
E-mail addresses: magrsv@hotmail.com, magda.vieira@ufpe.br (M.R.S. Vieira).

https://doi.org/10.1016/j.surfcoat.2019.04.040
Received 4 September 2018; Received in revised form 9 April 2019; Accepted 10 April 2019
Available online 12 April 2019
0257-8972/ © 2019 Elsevier B.V. All rights reserved.
R.G.C. da Silva, et al.
Fig. 1. Classifications of contact angle (CA) from the liquid-solid interaction.
Fig. 2. Illustration of droplet state according to the (A) Wenzel and (B) Cassie-Baxter models.
Cassie-Baxter reported the wettability on heterogeneous surfaces,
where the spaces available on the substrate due to the roughness are
filled with air, as shown in Fig. 2 [16]. This causes a decrease in the
energy of the interaction between liquid-solid, since air is an absolute
superhydrophobic material with a contact angle (θ) of 180°, which fa-
cilitates the bearing of droplet and increases the contact angle [17,18].
Therefore, increasing the fraction of trapped air also leads to the con-
tact angle becoming larger regardless of the type of surface.
According to Marmur [19], only the Cassie-Baxter regime is essen-
tial in order to obtain superhydrophobicity. However, the destabiliza-
tion of a heterogeneous interface can lead to the Wenzel regime. The
transition between the Wenzel and Cassie-Baxter regimes depends on
the size of the droplet and the parameters of the roughness. To stabilize
the three interfaces, a hierarchical structure on a micro- and nano-scale
is needed. Micro-asperities resist the capillarity effect, while nano-
roughness prevents nanodroplets from filling the valleys between as-
perities [20].
To prepare the surface roughness, this study used an acid attack
with hydrochloric acid in order to make micro-roughness and deposit a
layered double hydroxides film on the substrate so as to obtain nano-
roughness. The morphologies obtained in micro and nanoscale favors
the storage of oxygen molecules on the surface, as described in the
Cassie Baxter model [13,14,20].
The layered double hydroxides (LDHs) have as general formula [MII1-
III m-
xMx (OH)2][Ax/m.nH2O], where A
m-
represents an anion with valent
m−; n represents the number of water molecules, and MII and MIII re-
present di and trivalent cations, respectively. Due to their high porosity
and high adsorption property, LDHs films are important to increase the
surface area and the interaction with molecules of surface energy re-
ducing agent [21,22].
Chemicals such as thiol, silane and carboxylic acid have been used
as surface energy reducing agent to modify organic and inorganic rough
surfaces. The functional group of these organic molecules, which is
hydrophilic, interacts with the rough surface of the substrate while the
carbon chain, which is hydrophobic, is directed off the surface, thereby
reducing the surface energy [23].
Zhang et al. [24] manufactured superhydrophobic surfaces on alu-
minum substrates by acid etching using Beck's solution followed by
deposition of an LDH film to produce roughness on a micro and na-
noscale, respectively. As low energy surface agent, an ethanolic stearic
acid solution were used.
Escobar and Llorca-Isern [25] fabricated superhydrophobic surfaces
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Surface & Coatings Technology 369 (2019) 311–322
on aluminum by using an acid attack with hydrochloric acid solution to
produce surface roughness and lauric acid as a low energy surface
agent.
There is a wide range of potential applications of superhydrophobic
surfaces. These include applying them to support biomedical [26] and
anti-reflective actions [27]; to reduce fluid drag [28], in anti-freeze
[29] and for anti-biofouling [30] and anticorrosive actions [31].
Therefore, superhydrophobic coating has evoked great interest in re-
searchers in terms of its use both for purely academic activities and
because of its potential use in industrial applications. However, there is
a need for a better understanding of specific properties of surfaces, such
as their morphology, roughness and surface chemistry, all of which
affect the wettability and stability of coatings [32].
There are many studies focused on the development of super-
hydrophobic coatings in aluminum alloys, aiming at increasing corro-
sion resistance. However, few studies have investigated the effect of the
initial surface treatment on obtaining these properties [33–37].
In this sense, this research sought to investigate the influence of
three different initials surface treatments (sanded, blasted and un-
treated) on the 5052 aluminum alloy, in the results of contact angle,
sliding angle and corrosion resistance in saline medium, from sub-
sequent identical steps of chemical modification of the surface to obtain
superhydrophobic surface: acid etching in hydrochloric acid solution
(2 mol/L); chemical treatment in zinc nitrate in (0.1 mol/L) in the
presence of ammonium hydroxide; and finally, reduction of the surface
energy by using stearic acid (28 mmol/L). In addition, the immersion
corrosion tests were performed during 28 days to evaluate the coatings
behavior when exposed to aggressive saline medium.
2. Materials and methods
2.1. Materials
From a 5052 aluminum alloy plates, the composition of which in-
cludes: Si (0.5%); Fe (0.23%); Cu (0.002%); Mn (0,058%); Mg
(2.324%); Cr (0.176%), Zn (0.003%); Ti (0.013%) and the remaining
element Al, 20 mm × 20 mm × 3 mm specimens were fabricated. The
solutions used were: aqueous acid solution of HCl (2 mol/L), aqueous
solution of hexahydrate zinc nitrate (0.1 mol/L) in the presence of
ammonium hydroxide; an ethanolic solution of stearic acid (28 mmol/
L); and sodium chloride solution (0.6 mol/L).
R.G.C. da Silva, et al.
Fig. 3. SEM images with increase of 1000× of the aluminum alloy surface morphology (a) UT surface, (b) UT surface after the acid attack, (c) SD surface, (d) SD
surface after the acid attack, (e) BT surface and (f) BT surface after the acid attack.
2.2. Surface initial condition of aluminum alloy
Initially, the samples were cleaned with isopropyl alcohol and
acetone, sequentially, in an ultrasonic bath for 5 min, and then dried
with hot air. Three different conditions of surfaces were prepared: 1)
mechanical polishing with #320, #600 and #1200 abrasive paper of
SiC; 2) blasting with Al2O3 sphere (CMV GS-9075×); and 3) non-
treatment, used as received by the provider Metaltorque (São Paulo,
Brazil). The samples were identified with the letters SD, BT and UT to
represent the initial conditions of sanded, blasted and untreated sub-
strate, respectively.
2.3. Fabrication of the superhydrophobic surface of aluminum alloy
The samples were etched with acid solution of HCl (2 mol/L) for
30 min, rinsed with acetone and deionized (DI) water in an ultrasonic
bath for 3 min and then dried with hot air [37]. Based in the experi-
ments of Guo et al. [38], a solution of 2.975 g of Zn(NO3)2·6H2O was
dissolved in 100 ml of deionized water and 4 ml ammonium hydroxide
was added subsequently. The 5052 aluminum alloy plates were im-
mersed into the above mixture solution and heated at 70 °C for 180 min.
The products were washed with deionized water and dried at room
temperature. Finally, the aluminum alloy samples were modified by
immersing them in an ethanolic solution of stearic acid (STA) 1% (mass
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Surface & Coatings Technology 369 (2019) 311–322
fraction) for 90 min, then left at 80 °C in an oven for 120 min. The
samples were identified with the letters UT (ACM), SD (ACM) and BT
(ACM) to represent the conditions of untreated, sanded and blasted
substrate after chemical modification (ACM), respectively.
2.4. Sample characterization
2.4.1. Contact angle and sliding angle measurements
The water contact angle (CA) and sliding angle (SA) was measured
with 8 μL deionized water droplets at room temperature using a goni-
ometer (Biolin Scientific Attension) and OneAttension 3.0 analysis
software. At least five parallel measurements were made for each
sample, and the average value of the contact angles and sliding angle
were reported.
2.4.2. Morphology and composition characterizations
The morphology of the aluminum compounds on the alloy surface
was observed using a field-emission-type of scanning electron micro-
scope (SEM; Hitachi TM 3000). Morphologies of alloy surfaces after
etching with acid, modifying with zinc nitrate in alkaline medium and
after treating with stearic acid were obtained. The chemical composi-
tion of the surface before and after chemical modification with zinc
nitrate in alkaline medium was characterized by Energy Dispersive
Spectroscopy (EDS) for which a Hitachi TM 3000 X-ray energy
R.G.C. da Silva, et al. Surface & Coatings Technology 369 (2019) 311–322

Fig. 4. Topography analysis (1) before and (2) after acid attack for each initial condition (a) UT, (b) SD and (C) BT.

Table I obtained in duplicate using a computer-controlled electrochemical

Results from the roughness parameters before and after the acid attack. workstation (AUTOLAB PGSTAT 302N - interface NOVA) in NaCl so-
Roughness UT SD BT
lution (0.6 mol/L) at room temperature. The experiment was performed
parameters in a three-electrode cell system with a saturated calomel electrode
Initial Attacked Initial Attacked Initial Attacked (SCE) as a reference electrode, a platinum electrode as the counter
electrode, and a 1cm2 sheet of untreated aluminum alloy/super-
Ra (μm) 5.601 14.143 4.061 13.104 12.442 13.401
Rsk (μm) 0.750 0.230 0.701 0.167 0.195 0.104
hydrophobic aluminum alloy as a working electrode. Polarization
Rku (μm) 5.489 3.887 4.853 3.843 4.770 3.575 curves were recorded at a sweep rate of 1 mV s−1 from −1300 to
+1900 mV. Each electrochemical test was repeated three times to en-
sure good reproducibility. Images were obtained using an optical mi-
dispersive spectrometer associated with SEM was used. Roughness croscope (Zeiss Ax10 Zoom.V16) after the electrochemical tests to
parameters such as Roughness Average (Rsa), Skewness (Rssk), Kurtosis evaluate the modifications to the surface.
(Rsku) and the initial topographic image and images after the acid attack
were obtained by analysis in a confocal microscope (Zeiss Imager Z2m). 2.4.4. Immersion corrosion test
The experiments were carried out in glass containers with 1 L of
2.4.3. Electrochemical experiments NaCl solution (0.6 mol/L), where the specimens were immersed at same
The polarization curves of electrochemical experiments were height of solution during 1 month (28 days). The contact angle

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Fig. 5. Percentage weight loss of 5052 aluminum alloy from each initial surface condition.
Table II
The contents of Al and Mg elements from EDS analysis on the surfaces
after the acid attack (weight %).
Samples Al Mg
UT 97.6 2.4
SD 97.1 2.9
BT 97.4 2.6
measurement and the analysis of the surface morphology (by SEM)
were carried out after exposure for 14 and 28 days.
After removed from the system, four specimens were dried in hot air
for 5 min on each face and left at room temperature for another 5 min.
Subsequently, the contact angle measurements were carried out and the
specimens were returned to the respective systems.
3. Results and discussion
3.1. Roughness and topography analysis
Fig. 3 shows the surface morphology of 5052 aluminum alloy
samples from each initial surface condition before and after the acid
attack in HCl (2 M) which lasted for 30 min at room temperature.
Fig. 3a, c and e show, respectively, the morphology of the untreated,
sanded and blasted surfaces. The untreated surface is marked in the
horizontal direction from the rolling process to which it was submitted
when it was being produced. What can be seen on the sanded surface
are marks in the vertical direction resulting from the sanding process
which was used to make the surface uniform and to obtain a little initial
surface roughness. As to the blasted substrate, a surface with an irre-
gular texture is observed due to the blasting process with alumina
spheres. After the acid attack, all the samples presented a surface which
was evenly modified with high roughness due to the presence of micro-
scale cavities.
In Fig. 4 the topographic analysis, for which a confocal microscope
was used, shows the micro-roughness profile generated by the acid
attack. From the color histogram, it is possible to observe that the in-
itially sanded samples presented better uniformity in the micro
roughness obtained after the acid attack than other initial surface
conditions.
Table I displays the results of the roughness parameters before and
after the acid attack. The untreated and sanded surfaces presented the
greatest variations in the values of average roughness (Rsa) after the
acid attack. These ranged from 5.801 μm to 14.143 μm and from
4.061 μm to 13.104 μm, respectively. The blasted surface presented the
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Surface & Coatings Technology 369 (2019) 311–322
highest initial Rsa, namely 12.424 μm, due to its irregular texture and
after the acid attack, the value of Rsa increased to 13.383 μm, thus in-
dicating a smaller variation, when compared to that of the conditions of
the other surfaces.
The Skewness (Rssk) and Kurtosis (Rsku) parameters are related to
the modification in the shapes of the roughness. The reduction observed
in Rssk and Rsku values indicated that after the acid attack, the rough-
ness profile was altered. A decrease was observed in the height of peaks
and an increase in the depth of valleys [40]. The modification of the
Rsa, Rssk and Rsku parameters after the acid attack characterized the loss
of the initial characteristics of rolling, sanding and blasting.
Fig. 5. shows the percentage values of weight loss after the acid
attack. The untreated, sanded and blasted samples showed a decrease of
3.5%, 4.6% and 8%, respectively.
The greater mass loss observed for the blasted surface may be as-
sociated with its having a larger surface area occasioned by this treat-
ment, thereby generating a greater contact with the acid attack.
Processes that cause a high loss of mass are not interesting to meet
the economic demand for engineering because they can generate ad-
ditional costs, waste material and damage mechanical properties, de-
spite the probable appearance of high contact angles [41].
3.2. Composition and morphology analysis after chemical modification
Table II shows the EDS analysis for the three kinds of treatment of
the surface of the alloy. Note the presence of Al and Mg, elements that
are in the 5052 aluminum alloy.
Fig. 6 displays the SEM images of the modification to the surface
with zinc nitrate in alkaline medium for each sample.
The surface of untreated samples showed two different morpholo-
gies, as shown in Fig. 6: one has 3D flowerlike microspheres and the
other has nanowall-like structures. This suggests that the hierarchical
structure has formed on a micro- and nano-scale during this step. A
similar morphology was obtained by ZHANG et al. [24], Guo et al. [39],
and WANG et al. [42], who associated these deposits with the formation
of zinc oxide and layered double hydroxides (LDHs) that can be re-
presented by the formula Zn(1-x)Alx(OH)2NO3(x).yH2O, which corre-
spond to hydrotalcite. Morphologies similar to those detailed for the
untreated surface condition were also obtained for the sanded and
blasted samples.
The difference in the results of the EDS analysis, shown in Table II
and Table III, confirms that a chemical modification in each sample has
occurred due to the formation of LDHs and zinc oxide represented by
the decrease amount of aluminum and by the presence of zinc, oxygen
(from the zinc oxide) and nitrogen (from the nitrate).
R.G.C. da Silva, et al. Surface & Coatings Technology 369 (2019) 311–322

Fig. 6. SEM images of the LDH film for each sample with 1000× (1) and 2500× (2) magnification. (a) UT, (b) SD and (c) BT.

Table III It was possible to observe a deposition of layered double hydroxides

The contents of Zn, O, Al and N elements from EDS analysis on the surfaces after for all the samples, regardless of the surface initial condition. Fig. 7
hydrotalcite has been deposited (weight %). shows a cross-sectional view, which clearly demonstrates that a mul-
Samples Zn O Al N tilayer was assembled on the aluminum alloy substrate, with thickness
(th) in micrometers of the LDH film for all conditions.
UT 60.0 31.8 7.5 0.5 Studies carried out by Li et al. [43] have shown that the morphology
SD 59.5 29.6 10.6 0.3
of reached hierarchical structures on a micro and nanometric scale. Due
BT 70.4 23.9 3.6 2.1
to the layered structure with high porosity, the LDHs increases surface
area and adsorptive capacity, allowing more molecules of the stearic

Fig. 7. SEM images of the LDH film cross-sectional view for each sample with 350× magnification (a) UT, (b) SD and (c) BT.

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Fig. 8. SEM images of the aluminum alloy surface after treatment with stearic acid for each sample with 1000× magnification (a) UT, (b) SD and (c) BT.

Fig. 9. Reaction between the carboxyl group of stearic acid and the hydroxyl group (OH−) present in HDL film, forming aluminum stearate (salt) and water.

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Fig. 10. Graph of the contact angle before and after chemical modification with
stearic acid for each surface condition: UT, SD and BT.

acid to interact on the surface in the next step [44]. Fig. 12. Polarization curves in NaCl solution for the aluminum alloy before and
Fig. 8 shows the SEM images of the chemical modification with after chemical modification under UT, SD and BT conditions.
stearic acid for each sample. Comparing Fig. 8 and Fig. 6, it can be seen
there was no significant change in the surface morphology of any of the Table IV
specimens when treated with stearic acid, i.e. the same 3D morpholo- Corrosion potential and corrosion current density results obtained by using the
gies as described above were maintained. Tafel extrapolation.
The main function of stearic acid is to modify chemically the sur-
Surface condition Ecorr (mV/SCE) icorr (μA/cm2)
face, by repelling water. The LDH present the hydroxyl group (OH−) in
its structure, which reacts with the carboxyl group of stearic acid by an UT −822.13 ± 20.55 8.73 ± 0.43
acid-base reaction, forming aluminum stearate (salt) and water, as SD −882.51 ± 22.06 11.89 ± 0.59
shown in Fig. 9 [45]. The carbon chain, which is hydrophobic, is di- BT −1150.00 ± 28.75 6.39 ± 0.32
UT (ACM) −680.48 ± 17.01 1.24 ± 0.06
rected off the surface, thereby reducing surface energy, as can be seen SD (ACM) −672.54 ± 16.81 1.21 ± 0.06
through the measurement of the contact angle (Fig. 10) [23]. BT (ACM) −697.61 ± 17.44 1.62 ± 0.08
Fig. 10 shows the values of the contact angle for all surface treat-
ment conditions studied before and after chemical modification. The
chemically untreated surfaces presented contact angle values of 35°, 70°
and 61° obtained for the SD, BT and UT samples, respectively, thus

Fig. 11. Sequence of images illustrating the self-cleaning effect on the SD (ACM) surface.

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Fig. 13. Images by optical microscope after the electrochemistry test in NaCl (0.6 mol/L) for each sample with and without coating (a) UT, (b) SD and (c) BT.
characterizing the surfaces studied as hydrophilic. After chemical
modification with stearic acid, the SD and BT samples showed a contact
angle value higher than 150°, thereby characterizing the surfaces as
superhydrophobic, while the UT surface presented a value of 147°
which can be classified as hydrophobic.
It is not possible to observe a significant difference between the final
contact angles obtained on the sanded and blasted surfaces. However,
the results showed a tendency towards smaller contact angles for the
untreated specimens. This result can confirm the hypothesis that
roughness is a decisive parameter for obtaining superhydrophobic
surfaces, since the UT surface presented a more heterogeneous rough-
ness profile than the SD and BT ones after the acid attack, as can be
observed from the topographic analysis in Fig. 4.
The sliding test verified that the SD (ACM) and BT (ACM) samples
also presented a self-cleaning characteristic, with SA of 5.67 ± 1.42
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Surface & Coatings Technology 369 (2019) 311–322
and 5.70 ± 1.43, respectively. Fig. 11 shows a sequence of images il-
lustrating the self-cleaning effect on the SD (ACM) surface, which
presented the best results of CA and SA. The drop of water rolled off the
surface and removed the sand, preserving the surface dry after the
cleaning procedure.
Zhi et al. [46] fabricated superhydrophobic surfaces on blasted and
untreated aluminum plates. They reported that the roughness influ-
enced the durability test and the values of the contact angle. The re-
searchers found that blasted specimens presented greater contact angle
values of 150°, 158° and 155°, when stearic acid, heptadecafluoro-
1,1,2,2-tetrahydrodecyltrichlorosilane and hexadecyltriethoxysilane,
respectively, were used as surface energy reduction agents.
Li et al. [41] fabricated superhydrophobic surfaces of 5052 alu-
minum alloy in sanded samples, using HCl (4 M) to create roughness
and silane as the surface reduction agent. They obtained a contact angle
R.G.C. da Silva, et al. Surface & Coatings Technology 369 (2019) 311–322

Fig. 14. SEM images magnified at 500×(1) and 1000×(2) surface morphology of the coated specimens according to the exposure time in NaCl solution after (a)
14 days and (b) 28 days.

Fig. 15. Contact angle behavior on SD (ACM) sample according to the exposure time in NaCl solution (0.6 mol/L) (a) initial (b) after 14 days and (c) after 28 days.

Table V valued, as for example stearic acid, which was aim of this paper [7].
The contents of the elements (weight %) from EDS analysis on the super-
hydrophobic surface SD (ACM) and after immersion for 28 days in NaCl solu-
tion (0.6 mol/L). 3.3. Corrosion resistance of the fabricated superhydrophobic surface
Sample Al Zn O C Na Cl
The corrosion resistance property of 5052 aluminum alloy in dif-
SD (ACM) 4.30% 62.30% 22% 11.10% – – ferent conditions of surface treatment was analyzed by using po-
NaCl (0.6 mol/L) 1.30% 24% 15.70% 37.9 13.90% 7.70%
tentiodynamic polarization curves in NaCl solution (0.6 mol/L) at room
temperature, as shown in Fig. 12. The curves of the surfaces without
of 153° which was similar to the value obtained in this article, using a superhydrophobic effect showed a typical behavior of aluminum, there
lower concentration of hydrochloric acid solution. being a small active zone, followed by a passivation zone. The sub-
Zhang et al. [47] fabricated superhydrophobic coatings on alu- sequent increase in current density is associated with pitting corrosion
minum substrates through three sequential steps: anodizing procedure, [5,7].
deposition of LDH film and reduction of the surface energy with Resistance to corrosion is characterized by a lower corrosion current
fluoroalkyl silane. The researchers reached a contact angle of 153°. density (icorr) and the positive-going shift of the corrosion potential
Similar results were found in this present study for BT (ACM) and SD (Ecorr) [41,48]. Table IV shows the results of icorr and Ecorr from un-
(ACM) samples, using a simpler and faster procedure. Furthermore, coated samples (UT, SD and BT) and coated samples chemically mod-
silanes are efficient surface energy reduction agents, however they ified with LDH structure and stearic acid, which were obtained by the
present a high cost and hazards to the environment due to the presence Tafel extrapolation method. As can be seen, the higher contact angle
of fluorine. Therefore, others more sustainable substances are being value presented by the ACM samples resulted in the lower interaction of
the samples surface with the aqueous electrolyte (0.6 mol/L NaCl

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solution), delaying the electrochemical corrosion. Consequently, the
corrosion potential of all the coated samples increased and the anodic
current density decreased.
The corrosion resistance efficiency (IE) can be calculated in Eq. (1)
[49]:
IE = 100% × (i1 − i2)/i1 (1)
where i1 is the corrosion current density of the surface initial condition
tested (UT, SD or BT) and i2 is the respective corrosion current density
after chemical modification. IE means the corrosion resistance growth
rate of sample 2 compared with that of sample 1. Eq. (1) shows that, for
each surface treat condition, the results for IE were 85.80%, 89.82%
and 74.65%, respectively, for the UT, SD and BT samples.
The best combination of micro and nano-roughness and surface
energy reducing agent was observed for SD(ACM) sample, which can be
proven by the best results presented of CA, SA, Ecorr and icorr than
UT(ACM) and BT(ACM). The performance of SD(ACM) was related to
the surface initial treatment of sanding, since the other experimental
parameters were the same for all specimens. From the color histogram
(Fig. 4), it was possible to observe that the sanding process (Fig. 4b1) on
substrate presented uniform roughness, with lower variation of peaks
and valleys (Table I). After acid attack with HCl (Fig. 4b2), the micro
roughness obtained along of the surface was more homogeneous than
the two other conditions.
In addition, an analysis using an optical microscope was conducted
to confirm and qualify the anticorrosive character of the coatings after
the electrochemistry test for each sample, as shown in Fig. 13. Note that
all uncoated samples deteriorated throughout the area exposed to the
NaCl solution and this was evidenced by cavities and microcavities. On
the other hand, the images of the coated samples indicate that the SHP
coating regressed the corrosion process, evidenced by the greater in-
tegrity of the surface when compared to that of the uncoated surface.
The study by Lv et al. [48] also reported an increase in the corrosion
resistance of superhydrophobic coatings, which were obtained in pure
aluminum substrates modified by NaClO and silane, compared to that
of uncoated surfaces. Furthermore, the researchers verified a decrease
in the contact angle value of 165,4° to 148,1° and 34.4° to 0° for the
coated surface and pure aluminum, respectively, after immersion for
7 days in a NaCl solution.
This paper proposed to carry out the immersion corrosion test for a
longer time of exposure than Lv et al. [48], in a same concentration of
NaCl solution (0.6 mol/L). The test was carried out for the sanded
condition, due the best results of CA, SA and corrosion resistance effi-
ciency. Fig. 14 shows the morphology changed of the surface after
dipped 14 and 28 days. The degradation of the coating was evident over
the exposure time, which can be verified by the presence of excavations
and the loss of the initial morphology of 3D flowerlike microspheres.
Fig. 15 shows the most representative images of the contact angle
measurement according to the exposure time to NaCl solution (0.6 mol/
L).
After 14 days of immersion, the coating lost the superhydrophobic
character, but kept the hydrophobic behavior with average CA = 98°.
After 28 days, the surfaces of the coated samples presented a hydro-
philic behavior, with average CA = 79°. The dissolution of the coating
in saline medium lost the Cassie-Baxter model characteristics and left
the surface closer to the Wenzel regime, with consequent increase of the
wettability until hydrophilicity condition.
The EDS results in Table V identify changes in the elemental com-
position of the superhydrophobic initial surface and the one after
28 days of immersion in NaCl solution. The presence of the Na and Cl
elements, which had not been identified until then, shows that there
was adsorption and salt attack on the coatings.
4. Conclusions
Superhydrophobic surfaces in 5052 aluminum samples with
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Surface & Coatings Technology 369 (2019) 311–322
excellent corrosion resistance have been successfully prepared by a
simple and low-cost method of chemical modification using an acid
attack combined with passivation and stearic acid. For all conditions,
hierarchical structures on a micro- and nano-scale were obtained by
associating an acid attack with the formation of hidrotalcyte. The
wettability of the surfaces of the samples so obtained was greatly in-
fluenced by the initial treatment of the surface (UT, SD and BT). The
methodology applied to obtain a superhydrophobic surface led to an
increase in the contact angle for all initial treatment conditions of the
surfaces. The optimal superhydrophobic performance was obtained
with a contact angle of 154.27° for the sanded surface after it was
treated with stearic acid. This condition also showed the best perfor-
mance in corrosion tests, and presented the lowest value for the current
density of the corrosion, the highest value for potential corrosion and
an efficiency of resistance to corrosion of 89.82%. However, the sta-
bility of the coating was affected during immersion corrosion test in
NaCl solution (0.06 mol/L). After 28 days of exposure in saline medium,
the coating lost superhydrophobic character and presented hydrophilic
behavior, with CA of 79°.
Acknowledgments
This work was supported by: National Council of Scientific and
Technological Development (CNPq) and Laboratory of Composite
Materials and Structural Integrity of the Department of Mechanical
Engineering, Federal University of Pernambuco/Brazil.
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