Colloids and Surfaces A 599 (2020) 124934

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Colloids and Surfaces A

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

Development and application of a passion fruit seed oil microemulsion as T

corrosion inhibitor of P110 carbon steel in CO2-saturated brine
Aline V. Souzaa, Janaína C. da Rochab, J.A.C. Ponciano Gomesb, Luiz C.M. Palermoa,
Claudia R.E. Mansura,b,*
a
Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora Eloisa Mano, Laboratório de Macromoléculas e Coloides na Indústria de Petróleo (UFRJ/
IMA/LMCP), Brazil
b
Universidade Federal do Rio de Janeiro, Programa de Engenharia Metalúrgica e de Materiais /COPPE, Brazil

G R A P H I C A L A B S T R A C T

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

Keywords: One of the most important causes of corrosion in the oil industry is CO2 and the injection of corrosion inhibitors
Microemulsion is an economical way to prevent it. Recently, many efforts have been made to develop eco friendly corrosion
Corrosion inhibitors inhibitors. This work reports the development of ecological microemulsified systems based on passion fruit seed
Green inhibitors oil applied as corrosion inhibitors for carbon steel pipes P110 in synthetic brine saturated with CO2, at different
Carbon steel
temperatures and inhibitor concentrations. The inhibition efficiency was investigated by tests of weight loss,
CO2 corrosion
linear polarization resistance, electrochemical impedance spectroscopy and polarization curves. The gravimetric
measurements showed maximum efficiency of 975 %. The results of the electrochemical tests presented the same
trends: increased inhibition efficiency at higher microemulsion concentration and lower efficiency with higher
temperature. Based on Electrochemical parameters of polarization tests, the corrosion inhibition efficiency of the
microemulsion M8 exceeded 99 % and the presence of the microemulsion promoted a reduction of the anodic
and cathodic reactions involved in the corrosion process, characterizing the microemulsion as an adsorption
inhibitor. The study of the metal surface morphology by scanning electron microscopy and contact angle
measurement confirmed the ability of the microemulsion to form a film to protect the metal against attack by
electrolytes.

⁎
Corresponding author at: Universidade Federal do Rio de Janeiro, Instituto de Macromoléculas Professora Eloisa Mano, Laboratório de Macromoléculas e Coloides
na Indústria de Petróleo (UFRJ/IMA/LMCP), Brazil.
E-mail address: celias@ima.ufrj.br (C.R.E. Mansur).

https://doi.org/10.1016/j.colsurfa.2020.124934
Received 4 February 2020; Received in revised form 28 April 2020; Accepted 28 April 2020
Available online 04 May 2020
0927-7757/ © 2020 Elsevier B.V. All rights reserved.
A.V. Souza, et al.
1. Introduction
Corrosion is a problem that occur throughout the entire oil pro-
duction process, thus having a large economic impact in this industry.
The use of carbon steel in the metal structures and equipment is the best
option in terms of availability, hardness and cost-benefit [1]. Never-
theless, when this metal is used for oil and gas transportation at all
stages of production from downhole to surface equipment and proces-
sing facilities a harsh environment composed by carbon dioxide gas
(CO2), hydrogen sulfide (H2S), brine and oxygen, cause the severe
corrosion [2]. The presence of CO2 is one of the main corrosion factors
in the oil and gas industry, because its solubilization in water causes the
formation of carbonic acid (H2CO3), which although being a weak acid,
causes a pH reduction, leading to severe corrosion of steel pipelines and
equipment [3]. The corrosion caused by the presence of CO2 can be
uniform or localized (pitting). The consequences of these types of cor-
rosion include lower production due to damage to pipelines and en-
vironmental disasters due to leakage of crude oil [2,4].
The application of corrosion inhibitors is the most practical and
economic way to counteract corrosion caused by CO2 [2,4]. Generally,
the efficient corrosion inhibitors used by the oil industry are organic
compounds containing nitrogen, oxygen and/or sulfur with unsatura-
tions in their structures [5,6]. These compounds can be adsorbed onto
the metal surface and block the sites susceptible to corrosive attack [7].
The synthetic organic inhibitors are able to inhibit corrosion, but they
are highly toxic and thus considered harmful to the environment.
In reaction to the global appeal for the use of safer and ecofriendly
chemical products due to rising environmental problems, the search for
inhibitors classified as “green” has been growing. Green inhibitors are
considered to be low toxicity compounds that can be obtained from
inexpensive plentiful sources and eco-friendly. Several compounds have
been investigated as green corrosion inhibitors, among them extracts
from plants and fruits stand out, due to their wide availability, biode-
gradability and low cost [8,9]. Previous studies [7–12] have shown that
extracts from roots, leaves, bark and seeds are promising as corrosion
inhibitors.
The activity of corrosion inhibitors by adsorption depends on sev-
eral factors, such as electronic structure of the molecules, concentra-
tion, temperature and mode of adsorption on the metal surface.
Previous studies have shown that the action of corrosion inhibitors can
be maximized by the synergistic effect through the combination with
another component that can act at the metal/electrolyte interface
[2,13,14]. Therefore, under certain conditions, better results are
achieved when the inhibitor formulation contains intensifiers, such as
surfactants [13].
One way to combine different components in a same formulation is
through the microemulsified systems. These chemical systems are no-
teworthy for containing various microstructures that exercise relevant
roles on the adsorption phenomenon in interfacial systems, such as
corrosion inhibitors action. Microemulsions are obtained by mixing of
immiscible liquids with the addition of a surfactant, and in some cases
with a cosurfactant, resulting in a homogeneous system [15].
This article reports the development of an oil-in-water (O/W) mi-
croemulsion composed by passion fruit seed oil, surfactant polyoxyl 40
hydrogenated castor oil and a cosurfactant, obtained from natural
sources, and synthetic brine. The passion fruit seeds (yellow passion
fruit - Passiflora edulis sims) are a byproduct of fruit processing for juice
and are mostly discarded today. Like other vegetable oils, passion fruit
seed oil has a chemical composition based largely on fatty acids such as
linoleic, palmitic, oleic, linolenic, myristic and stereatic; tocopherols
and phenolic compounds [16–18]. These substances are rich in car-
boxyls, hydroxyls and carbonyls groups, and thus can interact with the
metal surface to promote a barrier against corrosion [7,10,19].
Although microemulsions have already been studied as corrosion
inhibitors, there are no publications on the investigation of the anti-
corrosive capacity of passion fruit seed oil. Passion fruit seed oil has a
2
Colloids and Surfaces A 599 (2020) 124934
composition similar to compounds with a proven inhibitory action
[19,20]; it comes from food industry residue, which contributes to cost
reducing of the final product, in addition to its; and it is biodegradable.
All these characteristics make the study of passion fruit seed oil highly
relevant.
The corrosion inhibition efficiency of the developed microemulsions
was evaluated by measurements of linear polarization resistance (LPR)
and electrochemical impedance spectroscopy (EIS), as well as by plot-
ting polarization curves and gravimetric measurements. The P110
carbon steel test specimens were analyzed by scanning electron mi-
croscopy (SEM) and contact angle measurements. The corrosion in-
hibition efficiency was ascertained in function of temperature and
concentration.
2. Experimental part
2.1. Materials
The microemulsions were prepared using the commercial nonionic
surfactants polyoxyl 40 hydrogenated castor oil (Kolliphor RH40) and
sorbitan monooleate (Span 80), obtained from Sigma-Aldrich/Merck
(São Paulo, Brazil). The polyoxyl 40 hydrogenated castor oil was used
like surfactant and the sorbitan monooleate like co-surfactant. The
passion fruit seed oil was obtained from Granoils (São Paulo, Brazil)
and its chemical analysis reported by the manufacturer is listed in the
Table 1. The synthetic brine was employed as the aqueous phase of the
microemulsion and in the gravimetric and electrochemical tests. The
synthetic brine presents a total dissolved salts (TDS) of 25,765 ppm and
its detailed composition is described in Table 2. The all salts were ob-
tained from Sigma-Aldrich (São Paulo, Brazil).
Determination of hydrophilic-lipophilic balance (HLB) of the oil
phase (passion fruit seed oil) was performed with two nonionic sur-
factants, polyoxyethylene (80) sorbitan monooleate (Tween 80) and
Span 80, both acquired from Sigma Aldrich (São Paulo, Brazil). Finally,
the composition of the P110 carbon steel used in the tests is reported in
Table 3.
2.2. Methods
2.2.1. Determination of hydrophilic-lipophilic balance (HLB) of passion
fruit seed oil
The HLB of the passion fruit seed oil was determined in order to
define the most suitable surfactant (or mixture of surfactants) to obtain
the microemulsion. The method used was described by Zanin [21] and
consisted of preparation of oil emulsions, obtained by mixing the sur-
factants (with known HLB values) in variable proportions, to reach a
defined HLB values. The emulsions were prepared under magnetic
stirring for 15 min, followed by resting for 24 h, at room temperature.
The HLB value of the oil was defined by observing the emulsion’s sta-
bility in relation to a reference emulsion with greater homogeneity, i.e.,
one that had no irregular aspect or phase separation.
Emulsion samples weighting 50 g were prepared from the aqueous
solutions of the mixtures of the nonionic surfactants Span 80 and Tween
80, with HLB values of 4.3 and 15, respectively. The concentration of
the surfactant mixture was fixed at 5% (v/v) and the oil concentration
at 10 % (v/v), both in relation to the total weight of the three
Table 1
Physico-chemical parameters of passion fruit seed oil.
Chemical quality parameters Specification Results
Density (g/mL) 0.910–0.929 0.918
Acidity (mg KOH/g) <1 0.98
Peroxide index (meq/kg) < 10 2.93
Iodine index (Wijs) 90 - 135 133.16
Saponification index (mg KOH/g) 190 - 220 196.06
A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Table 2 microemulsions have affinity for water and are insoluble in the oil
Brine composition. phase, while the opposite holds for water-in-oil (W/O) emulsions [24].
Composition Concentration (mg.L−1)
2.2.4. Gravimetric measurements
Na+/K+ 11,309 The weight loss evaluation was performed with test specimens
Ca+2 117
(coupons) with dimensions of 10 × 10 × 5 mm and a central hole with
Mg+2 109
SO42− 5 diameter of 3 mm. The coupons were previously polished with 300–600
HCO−3 64 mesh sandpaper, washed with alcohol, dried in hot air, kept for 10 min
Cl− 17,756 in an ultrasound bath and then weighed on an analytical balance
TDS 29,360 (0.1 mg precision). The brine (with and without inhibitor) was pre-
viously saturated with CO2 gas during 1 h at a flow of 200 mL/min,
until reaching a minimum oxygen concentration of 50 ppb and pH
Table 3
around 3.8. The coupons were immersed in a closed system, in the
P110 carbon steel composition.
absence of oxygen, for 72 h. Thereafter, the coupons were cleaned to
Composition Concentration (%) remove the corrosion products using Clark’s solution, which is com-
posed of hydrochloric acid (HCl), antimony trioxide (Sb2O3) and stan-
C 0.26
Si 0.24 nous chloride (SnCl2). Then the coupons were washed with water and
Mn 1.08 ethanol, placed in an ultrasound bath for 10 min, dried with hot air and
P 0.014 kept in a vacuum desiccator for 40 min, followed by weighing. The all
S 0.001
tests were performed in triplicate.
Cr 0.31
Ni 0.03
The weight loss was measured according to the ASTM G31-72
Mo 0.06 standard. The corrosion rate (CR) was calculated from the following
Cu 0.01 equation:
V < 0.01
(K . W )
CR =
A. t . ρ (2)
components (water, surfactant and oil phase). Therefore, the water 4
Where K is a constant (8.76 × 10 ), W is the weight loss in grams, A is
weight was 42.5 g, the oil weight was 5 g and the weight of the sur-
the exposed surface area in cm2, t is the exposure time in hours, and ρ is
factant mixture was 2.5 g. The weights of the surfactants in the mixture
the density of the material in g/cm3 (ρ = 7.86 g/cm3 for carbon steel).
were calculated according to Eq. (1), to obtain emulsions with known
The inhibition efficiency (IE%) was calculated from the corrosion rates
HLB values in the range from 4.3 to 15.
using the following equation:
(HLB * − HLB b)
Surfactant Concentration (%) α = x 100 CR − CRi ⎞
HLB α − HLB b (1) IE (%) = ⎛ . 100
⎝ CR ⎠ (3)
Where:
Where CR and CRi are the corrosion rates in mm/year of the coupons in
α – surfactant a
the absence and presence of the inhibitor, respectively.
b – surfactant b
HLB* - desired HLB
2.2.5. Electrochemical measurements
HLB a –HLB value of surfactant a
The electrochemical tests were performed with an Autolab-PGSTAT
HLB b – HLB value of surfactant b
302 potentiostat (Metrohm, Switzerland), controlled by the NOVA 1.11
program. Measurements were carried out by using a glass test cell with
2.2.2. Obtaining the ternary phase diagrams volume of 500 mL containing three electrodes: reference electrode,
The microemulsion composition was selected based on the con- counter electrode (composed of a platinum wire) and working electrode
structing of ternary phase diagrams, through the titration method de- (composed of P110 steel). The working electrodes (WE) were prepared
scribed by Kalaitzaki et al. and Carvalho et al. [22,23]. The titration by embedding steel rods in epoxy resin with exposed a surface area of 1
was carried out by progressive addition of brine in samples containing cm2. The WE was previously polished with 300–600 mesh sandpaper,
specific surfactant/cosurfactant:oil mixtures, in proportions from 1:9 to cleaned with ethanol and dried with hot air. To minimize the formation
9:1 by weight, for 11 days. The samples were inspected visually after of cracks, enamel was applied at the metal/inlayed resin interface. All
each synthetic brine addition and were classified as liquid or viscous tests were performed in duplicate to guarantee the reproducibility of
microemulsion, liquid or viscous macroemulsion, gel, or as phase se- the results.
paration system. The electrochemical measurements were performed after immersing
the electrodes for 1 h in the test solution, until the potential stability,
2.2.3. Preparation and characterization of the microemulsions determined by OCP (open circuit potential) X time. Then the linear
The microemulsions were prepared by magnetic stirring of the polarization resistance (LPR) measures were obtained by polarization of
water/oil/surfactant/cosurfactant mixtures, in the proportions selected the working electrode from +15 to −15 mV in relation to the corrosion
according to the ternary phase diagrams. These microemulsions were potential (Ecorr), at a scanning rate of 0.333 mV/s-1.
characterized by droplet size distribution of the dispersed droplets and The electrochemical impedance spectroscopy (EIS) measurements
the solubility parameters. were carried out in a frequency range of 10KHz −10 mHz, distributed
The microemulsions were stored for 30 days at room temperature in logarithmic form in 50 points, using a signal with amplitude of
(25 °C) in order to evaluate their stability. Every 7 days, the size dis- 10 mV. The polarization curves were performed in the potential range
tribution of the dispersed droplets was assessed, in triplicate, by dy- from −250 mV to +250 mV, with a scanning rate of 0.333 mV/s-1. The
namic light scattering using a Zetasizer Nano ZS (Malvern Instruments, IE values via the measures of LPR, EIS and polarization curves were
UK). determined from the following equations:
The evaluation of the microemulsions solubility allowed classifying
Rpi − Rp
the type of emulsion formed based on the behavior of the sample in IE =
contact with each of its phases separately. Oil-in-water (O/W) Rpi (4)

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A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

R cti − R ct
IE = . 100
R cti (5)
CR − CRi
IE (%) = ⎛ ⎞ . 100
⎝ CR ⎠ (6)
Where, Rpi and Rp are the polarization resistance values with and
without the inhibitor; Rcti and Rct are the charge transfer resistance
values with and without the inhibitor, respectively; and CR and CRi are
the corrosion rates, in mm/year, with and without the inhibitor, re-
spectively.
2.2.6. Morphological analysis
2.2.6.1. Scanning electron microscopy (SEM). The surface morphology
of the P110 carbon steel coupons was analyzed by SEM, using a Vega 3
SBH microscope (Tescan, Czech Republic) with voltage of 20 kV. The
coupons were the same ones used in the weight loss tests, with inhibitor
concentration of 1.5 % (v/v) at temperatures of 25 °C, 40 °C and 60 °C.
The coupons were dried and kept in the vacuum desiccator until the
SEM analysis.
2.2.6.2. Contact angle measurement. The contact angles of the surfaces
coupons were measured after the weight loss experiments, according to
the method described by Cen [25]. The coupons were dried and then a
droplet (2 μL) of distilled water was allowed to fall on the metal surface
to obtain the contact angle between the metal and water, which was
measured with a Pat-1 M tensiometer (Sinterface, Germany), by
applying the sessile drop method. The measures were performed in
duplicate on different areas of the coupon, and the final contact angle
reported is the average of the two measurements.
3. Results and discussion
3.1. Determination of hydrophilic-lipophilic balance (HLB) of passion fruit
seed oil
and then evaluated the mixture aspect. This evaluation was based on
the phase equilibrium involving microemulsion systems established by
Winsor [27]. There are four systems: Winsor I, an O/W microemulsion
in equilibrium with an excess of the organic phase; Winsor II, a W/O
microemulsion in equilibrium with an excess of water; (iii) Winsor III, a
three-phase system with a microemulsion normally in equilibrium with
the organic phase and excess of water; and Winsor IV, a macro-
scopically single-phase system composed only of the microemulsion.
The data obtained for these mixtures were plotted in an equilateral
triangle where each point inside the diagram corresponded to the
proportions defined for the mixture components. Fig. 1 depicts the
pseudo-ternary diagrams obtained for the proportions of the surfactants
(Kolliphor RH40)/cosurfactant (Span 80) of 70:30 (HLB = 11) and
75:25 (HLB = 12). These proportions were chosen based on the results
obtained in the measurement of the HLB value of the passion fruit seed
oil, which was in the range of 11–12.
The pseudo-ternary diagrams allow distinguishing the presence of
translucent fluids (such as liquid and viscous microemulsions), opaque
fluids (such as liquid and viscous macroemulsions), and gels (systems
characterized by high viscosity). Fig. 1b shows that the 75:25 surfactant
proportion resulted mainly in viscous and gel systems, with the region
of liquid microemulsion being relatively small. In contrast, the diagram
referring to the surfactant/cosurfactant proportion of 70:30 (Fig. 1a)
presented a greater microemulsion region. This indicates that the
mixture had the greatest compaction of the surfactant/cosurfactant at
the water/oil interface, which reduced the interfacial tension and thus
resulted in smaller and more uniform droplets, characteristic of mi-
croemulsions [23,28].
Therefore, were selected compositions of the liquid region of the O/
W microemulsion with the 70:30 surfactant/cosurfactant mixture
(Fig. 1a), with different fractions of oil, water and surfactant/co-
surfactant mixture. The values of the selected microemulsion compo-
sitions are reported in Table 5.
3.3. Characterization and stability of microemulsions

According to Fernandes [26], the HLB value of oil is measured by The microemulsions prepared based on the compositions shown in
preparing emulsions of surfactant mixtures with known HLB values, Table 5 were characterized according to the chemical character of its
with the HLB value of the oil being that of the surfactant mixture that external phase and also by the droplet size distribution.
forms the most stable emulsion. A droplet of each microemulsion was added to each of two solvents:
The HLB value of the passion fruit seed oil was determined by one hydrophilic (distilled water) and the other hydrophobic (passion
testing 10 emulsions with distinct HLB values, using mixtures of the fruit seed oil), in order to investigate the affinity of the external phase
surfactants Span 80 (HLB = 4.3) and Tween 80 (HLB = 15). The sta- of the microemulsion for these fluids. The chosen microemulsions had
bility results are reported in Table 4. The water/passion fruit seed oil greater affinity for the aqueous solvent than the hydrophobic one,
emulsions with HLB values of 11 and 12 were homogeneous, indicating where the totally insoluble drop formation was observed, as shown in
that the oil HLB value is in this range. Fig. 2. This indicates that all the microemulsions formed were of the O/
W type.
3.2. Obtaining the ternary phase diagrams and selecting the microemulsion The droplet size of the dispersed phase a microemulsions was
measured during 30 days at room temperature. The results are shown in
The microemulsion systems composition was obtained by con- Fig. 3. The microemulsions M1, M2 and M3 presented average droplet
structing pseudo-ternary phase diagrams. This method consisted of sizes between 22.8 and 44.35 nm. However, microemulsions M2 and
preparing binary mixtures followed by addition of a third component, M3 showed signs of destabilization after aging for two weeks. Micro-
emulsions M4, M5 and M6 showed average droplet sizes ranging from
Table 4 64.5 to 75.0 nm. However, although M4 and M5 had been chosen based
Results of HLB determination tests of the passion fruit seed oil. on the liquid microemulsion regions of the pseudo-ternary diagram,
Emulsion HLB mixture Results when preparing a larger quantity than used to construct the diagrams, it
was observed consistency of viscous microemulsions. The same beha-
1 5 Phase separation vior was observed for microemulsion M9, which presented droplet size
2 6 Phase separation
distribution between 48.0 and 51.5 nm. The microemulsion M8 pre-
3 7 Phase separation
4 8 Phase separation sented a monodispersed distribution, with droplet size range of
5 9 Phase separation 48.6–54.5 nm, which remained stable during the entire 30-day study
6 10 Phase separation period. For microemulsion M7, the average droplet size on the first day
7 11 Homogeneity of analysis was 51.52 nm, but destabilization occurred after the first
8 12 Homogeneity
week of observation.
9 13 Phase separation
10 14 Phase separation Based on the results obtained after stability tests microemulsion M6
and M8 were chosen for the corrosion inhibition analysis, due to its

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A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Fig. 1. Pseudo-ternary diagrams of the systems containing the components brine/ passion fruit seed oil/surfactant/cosurfactant: (a) 70:30; (b) 75:25.

Table 5 3.4. Gravimetric tests

Selected microemulsion compositions.
Oil (% v/ Brine (%v/ Surfactant/Cosurfactant (%
The corrosion rates from of immersion test of the P110 carbon steel
v) v) v/v) coupons during 72 h in brine saturated with CO2, in the presence and
absence of the microemulsions, were calculated as listed in Table 6.
Microemulsion 1 (M1) 1.8 82 16.2 The considerable increase of the IE by adding the microemulsion
Microemulsion 2 (M2) 1.2 88 10.8
Microemulsion 3 (M3) 2.4 76 21.6
systems M6 and M8 confirmed the ability to inhibit corrosion of the
Microemulsion 4 (M4) 13.2 56 30.8 carbon steel analyzed. The best corrosion rates obtained were in the low
Microemulsion 5 (M5) 8.40 72 19.6 corrosiveness classification (uniform CR > 0.025 mm/y), according to
Microemulsion 6 (M6) 10.8 64 25.2 the NACE RP-07-75 standard (1999) [29].
Microemulsion 7 (M7) 5.6 72 22.4
In the presence of microemulsion M8, there was a significant decline
Microemulsion 8 (M8) 6.4 68 25.6
Microemulsion 9 (M9) 64 7.2 28.8 of the corrosion rate with the increase in the inhibitor concentration. In
counterpart, with rising temperature, the corrosion rates were higher
due to reduced action of the inhibitor. In turn, in the presence of M6,
good stability, monomodal droplet size distribution and also because of the IE declined both with the increase in the inhibitor concentration
its liquid aspect, as determined from the pseudo-ternary diagrams. and elevation of temperature of the system.
Although microemulsion M1 had good stability, it was not chosen be- The improvement observed in the IE caused by the increased in-
cause of its low oil concentration (1.8 % (v/v)) compared to the other hibitor concentration in the tests with microemulsion M8 can be at-
microemulsions. tributed to the fact that with higher concentration, there is a larger
quantity of inhibitor adsorbed on the metal surface and a smaller
number of active sites available for corrosion reactions [2]. However,

Fig. 2. Solubility test results: (a) water (b) oil.

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A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Fig. 3. Particle size distribution curves of the microemulsions: (a) M1; (b) M2; (c) M3; (d) M4; (e) M5; (f) M6; (g) M7; (h) M8; (i) M9.

Table 6
Data obtained from the gravimetric measurements.
25 °C 40 °C 60 °C

Concentration (% v/v) CR (mm/y) IE (%) CR (mm/y) IE (%) CR (mm/y) IE (%)

Blank – 0.4806 ± 0.0008 – 0.6802 ± 0.0002 – 0.8322 ± 0.0006 –

M6 0.5 0.1098 ± 0.0054 77.15 0.0979 ± 0.0009 85.60 0.1666 ± 0.0035 79.98
1.0 0.1204 ± 0.0019 74.94 0.1348 ± 0.0010 80.18 0.2059 ± 0.0005 75.25
1.5 0.1574 ± 0.0007 67.24 0.2282 ± 0.0023 66.45 0.3079 ± 0.0007 63.00
M8 0.5 0.0401 ± 0.0009 91.66 0.0685 ± 0.0001 89.92 0.1024 ± 0.0004 87.69
1.0 0.0135 ± 0.0003 97.19 0.0425 ± 0.0009 93.75 0.0738 ± 0.0015 91.13
1.5 0.0120 ± 0.0001 97.50 0.0189 ± 0.0006 97.22 0.0392 ± 0.0008 95.29

some researchers have reported a decline in the performance of cor-
rosion inhibitors with rising concentration [2,30,31]. The action of the
inhibitor on the metal surface can be limited by the concentration,
because the presence of many molecules can hinder their reach at the
active site on the metal surface, or there can be disordered adsorption of
the inhibitor, which in turn causes steric hindrance, impeding the ac-
tion of the inhibitor molecules at the unprotected sites of the metal
surface [2,14]. This phenomenon explains why microemulsion M6
presented decreasing inhibition efficiency with rising concentration.
This indicates that the optimal concentration of the corrosion inhibitor
is 0.5 % and increasing it would not result in better efficiency.
In general, the IE values obtained for microemulsion M8 were much
better than those obtained for M6. For example, there was a difference
of approximately 20 % in the maximum efficiency achieved by M8
versus the maximum efficiency attained by M6 in the tests carried out at
room temperature. So, according to the best results obtained for mi-
croemulsion M8 in the weight loss tests, it was chosen for the electro-
chemical tests and morphological analysis.
3.5. Electrochemical measurements
3.5.1. Measurements of open circuit potential (OCP) and linear
polarization resistance (LPR)
The variation of OCP with time for the P110 steel immersed in CO2-
saturated brine at different concentration of M8 are shown in Fig. 4.
This Figure shows that, regardless of the inhibitor concentration M8, at
the beginning of the test, the OCP value shifts towards more active
values, and after some time (1 h), it reaches a steady state value. The
difference in EOCP in the absence and presence of the formulation in-
dicates that the API P110 surface was covered and protected by the
inhibitor adsorption. The Fig. 4 also revealed an initial sharp increase in
corrosion potential with decrease of temperature, the highest value of
the potential variation was observed for the concentration of 0,5%(v/v)
of microemulsion M8 with temperature of 40 °C.
The values of potential (E) and current density (icorr) obtained in the
LPR test were plotted and the graphs are depicted in Fig. 5. Table 7
shows the values of polarization resistance (Rp) and IE. The Rp value of
each test was obtained by the angular coefficient of the lines and the IE
was calculated using these Rp values in Eq. (4). According to Table 7,
the Rp values increased with the addition of microemulsion M8, in-
dicating the action of the inhibitor at the metal/electrolyte interface.
Note that Rp and IE both increased with the increase of inhibitor con-
centration, in accordance with the results found in the weight loss tests.
For higher concentrations, greater polarization resistance on the metal
surface was observed, indicating that the inhibitor adsorption was more
efficient, reducing the corrosion intensity.
3.5.2. Electrochemical impedance spectroscopy (EIS)
The Fig. 6 and 7 contains the impedance diagrams (Nyquist and
Bode plots, respectively) from the tests performed in the absence and
presence of the inhibitor M8 with different concentrations and tem-
peratures.
The Nyquist diagrams, presented three archs: a capacitive arch,
related to the relaxation of the double layer, followed by an inductive

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A.V. Souza, et al.
Fig. 4. OCP plots for API P110 carbon steel in brine saturated with CO2 in the presence and absence of microemulsion M8: (a) 25 °C; (b) 40 °C and (c) 60 °C.
arch and another capacitive arch at low frequency. The phenomena
occurring at medium frequency can be associated with the relaxation of
adsorption of intermediate species from the dissolution of the carbon
steel, such [FeOH]ads, or inhibitor molecules on the metal surface
[32,33]. The second capacitive arch at low frequency could be asso-
ciated with the deposition of the corrosion product on the steel surface,
forming a resistive barrier [25].The impedance diagrams showed si-
milar behavior at all temperatures and concentrations analyzed and,
therefore, presented the same corrosion mechanism. In general, the
addition of microemulsion M8 resulted in a substantial increase in the
diameters of the capacitive semicircles and a considerably enlarged of
them was observed as the concentration of the corrosion inhibitor in-
creased for all evaluated temperature. This indicates the ability of the
microemulsion M8 to act at the electrolyte/surface interface and pro-
mote protection of the carbon steel.
In the Bode θ versus log f plots, it can be seen that there are three-
time constants for all conditions analyzed, which corresponded the one
peak in the high frequency range followed by a valley and another peak
in the medium and low frequency range, respectively. The addition of
inhibitor increases the maximum phase angle and amplifies the angle
signal, indicating the compact inhibitor film was formed with less
porosity. Furthermore, the maximum phase angle and low frequency
impedance modulus increases with the increasing inhibitor concentra-
tion, as shown in Bode plots.
The electrochemical impedance parameters were determined by the
semicircle fitting method. The obtained data from various impedance
profiles were fitted into an equivalent circuit (Fig. 8) to model the
impedance spectra on the carbon steel/solution interface in the absence
7
Colloids and Surfaces A 599 (2020) 124934
and presence of inhibitors, using Zsimpwin software. The equivalent
circuit was consisted by the solution resistance (Rs), constant phase
elements, representing the double-layer capacitance (CPEct) and the
capacitance of scale on the metal surface (CPEf), resistance for film of
corrosion products (Rpore), charge transfer resistance (Rct), inductance
resistance (RL) and inductance (L).
The electrochemical parameters obtained by the fitting method
were: electrolyte resistance (Rs); charge transfer resistance (Rct), con-
stant phase element of double layer (CPE); fit error (chi-squared) and
parameter n, which indicates different physical phenomenon, including
surface roughness, inhibitor adsorption and/or desorption and porous
film formation, and the values of ‘n’ lie between 0 and 1 (when n = 1, it
means that the capacitor is in an ideal state, and the surface of the metal
is very homogeneous). The electric double-layer capacitance (Cdl) was
calculated by the following equation:
Cdl = Y0 (2πfmáx )n − 1 (7)
Where, Y0 is the magnitude of CPE and ƒmax represents the frequency
value at the maximum imaginary fragment of the impedance. The va-
lues are shown in Table 8.
The Table 7 clearly shows that the presence of microemulsion M8
caused a significant increase in the value of Rct, suggesting that the
inhibitor retarded the transfer of electrons at the electrode/electrolyte
interface, decelerating the corrosion reactions and protecting the metal.
The chi-squared values vary from 0.0014 to 0.0086, indicating a good
fitting to the equivalent circuit. These lower values of chi-squared
suggests that the fitted data is in agreement with the experimental data.
The reduction of the Cdl in the tests with the inhibitors was
A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Fig. 5. LPR plots for API P110 carbon steel in brine saturated with CO2 in the presence and absence of M8 microemulsion: (a) 25 °C; (b) 40 °C and (c) 60 °C.

Table 7 species available, which can imply tighter compaction of the species on
Electrochemical parameters of OCP and LPR tests.a the double layer, protecting the metal surface more effectively [34,35].
LPR OCP
The maximum IE values determined for each testing temperature
were very close to each other, indicating that microemulsion M8
Conc. (% v/v) Rp (Ω. cm2) IE (%) -Eocp (mVAg/AgCl) functions as a corrosion inhibitor for P110 carbon steel.

25 °C Blank 187.31 – 673

0.5 766.12 75.55 641 3.5.3. Polarization curves
1.0 1055.22 82.24 635 The anodic and cathodic polarization curves of the P110 carbon
1.5 2389.09 92.15 616 steel in brine saturated with CO2, for different concentrations of mi-
40 °C Blank 89.29 – 674
croemulsion M8 and temperatures, are shown in Fig. 9. For each ana-
0.5 594.66 84.98 617
1.0 923.78 90.33 618 lysis, data were obtained referring to: corrosion current density (Icorr),
1.5 943.37 90.53 626 the Stern-Geary equation (Eq. 8) was used, according to others authors
60 °C Blank 55.80 – 668 [12,36,37]; corrosion potential (Ecorr); slopes of the anodic (ba) and
0.5 175.30 68.16 648 cathodic (bc) curves, obtained by extrapolating the Tafel curves using
1.0 235.76 76.33 638
1.5 364.97 84.71 644
the Rp value obtained by the LPR test; corrosion rate (CR); and corro-
sion inhibition efficiency (IE). These are listed in Table 9.
a
Values obtained by duplicate tests.
|ba|. |bc |
Icorr =
2.303. (|ba|. |bc |). Rp (8)
compared with the blank tests and showed that the thickness of the
double layer increased in function of the adsorption of the inhibitor According to the literature [12,38,39], it is not advisable to perform
molecules on the surface. This can be explained by the fact that Cdl is Tafel extrapolation when the cathodic or anodic branch presents more
inversely proportional to the thickness of the double layer, although than one reaction, as observed in the anodic reactions under the con-
other factors can also influence the value of Cdl, such as the local di- ditions with addition of the microemulsion M8 at temperatures of 25
electric constant and composition of the adsorbed molecules [2]. The and 40 °C. However, due it is the most common method used to de-
values of Cdl were smaller in the tests with higher inhibitor con- termine electrochemical parameters obtained via polarization curves,
centrations, suggesting that these systems have a larger number of this approach was applied for purposes of comparison.

8
A.V. Souza, et al.
Fig. 6. Nyquist plots for API P110 carbon steel in brine saturated with CO2 in the presence and absence of microemulsion M8: (a) 25 °C; (b) 40 °C and (c) 60 °C.
The addition of microemulsion M8 to the system promoted a sub-
stantial reduction of the current density, indicating the inhibitory ac-
tion of these molecules on the metal surface. The values in Table 8 show
that in the presence of the inhibitor, the Icorr value declined with in-
creasing concentration, while the values of IE increased. However,
there was a drop in the IE value with rising temperature. These results
had the same trend as those obtained in the gravimetric tests. In other
words, there was a positive effect on the protection of the metal with
higher concentration of microemulsion M8 in the system and depen-
dence of the inhibition efficiency in relation to the temperature.
The decline of the IE value with the increase in temperature can be
attributed to a possible shift in the adsorption/desorption equilibrium
toward desorption of the inhibitor from the metal surface due to the
thermal agitation, leading to the hypothesis that the inhibitor adsorp-
tion happens via physical interactions [40,41]. Another factor that can
explain the influence of temperature on the IE is the droplets size of the
dispersed phase in the microemulsion. Microemulsions contain droplets
with reduced curvature, and these structures have greater areas for
interfacial contact, and hence can improve the interaction between the
fluid and the surface. The sizes of these dispersed droplets will influence
the surface coverage efficiency. The smaller the droplet size, the better
will be the interaction with the surface as well as the droplets’ orga-
nization and compaction in order to form a protective film [15,42]. One
of the factors that can destabilize the microemulsion and influence the
droplet size is temperature. Increasing temperature, there is a reduction
in viscosity of the system, which increases the mobility of the dispersed
9
Colloids and Surfaces A 599 (2020) 124934
droplets and its diffusion in the continuous phase (water), enabling the
droplets to coalesce into larger ones. The larger droplet size impairs the
uniform deposition/adsorption on the surface, leaving voids open to
attack by electrolytes [15,43].
The anodic and cathodic polarization curves show a reduction of the
current densities with the addition of the microemulsion system. The
changes in the values of bc and ba in the presence of the microemulsion
indicate the control of the inhibitor in the anodic and cathodic reactions
involved in the corrosion process. Therefore, these results showed that
the adsorption of the inhibitor on the metal surface delayed the metal’s
dissolution and the cathodic process, and consequently diminished the
corrosive process [16,38,44].
3.6. Morphology
3.6.1. SEM
The SEM images in Fig. 10 show the metal samples before and after
immersion in the brine saturated with CO2, with and without 1.5 % (v/
v) of microemulsion M8, at temperatures of 25 °C, 40 °C and 60 °C. The
surface of the P110 steel before immersion (Fig. 10a) was smooth, with
polishing lines. After immersion for 72 h in the solution free of the in-
hibitor (Figs. 10b, 10c and 10d), the surface was attacked, with obvious
disappearance of the polishing lines and increased surface roughness.
The absence of pits and homogeneous attack observed on the metal
surface can be characterize a uniform corrosion. In the presence of 1.5
% (v/v) of the microemulsion M8 at 25 °C and 40 °C (Figs. 10e and 10f),
A.V. Souza, et al.
Fig. 7. Bode and Phase angle plots for API P110 carbon steel in brine saturated with CO2 in the presence and absence of microemulsion M8: (a) 25 °C; (b) 40 °C and
(c) 60 °C.
the surface remained relatively smooth, with the presence of some
vestiges of salts and polishing lines. In the test at 60 °C, the surface had
a slight increase in roughness compared to the others, but it was still
possible to identify polishing lines, indicating protection of the metal.
These results corroborate those obtained in the gravimetric and elec-
trochemical tests, about protective film formation due to adsorption of
the molecules present in the microemulsion M8 on the metal surface.
3.6.2. Contact angle analysis
The contact angle measurement allows understanding the wett-
ability degree when solid and liquid surfaces interact. In general, the
anticorrosion performance of inhibitors is associated with the hydro-
phobicity of the inhibitor films, determined by how the corrosion in-
hibitors interact with the metal surface by means of the polar groups
present in its structures, leaving the apolar parts in contact with the
medium. The measurement of the contact angle between the solid and
liquid enables evaluating the hydrophobicity of these films [45,46].
Fig. 11 shows there was an increase of the contact angle in the presence
of the microemulsion M8, indicating adsorption on the interface, and
consequently protection of the surface from attack of the electrolytes.
The largest contact angle (89.7°) was observed in the test at room
temperature, indicating better surface coverage with strong hydro-
phobic properties. The hydrophobic inhibitory film can effectively
isolate metal surface from corrosive medium, inhibiting the corrosion of
carbon steel [25]. This is in accordance with the results of the gravi-
metric and electrochemical tests. The larger the contact angle with the
surface, the greater will be the coverage, and thus the lower the cor-
rosion rate will be. The formation of the adsorbed inert barrier isolates
the steel surface from the electrolyte, promoting the growth of a
10
Colloids and Surfaces A 599 (2020) 124934
protective layer on the steel surface, as also indicated by the SEM
images.
3.7. Inhibition mechanism
The microemulsion M8 is composed of surfactant, cosurfactant and
passion fruit seed oil, and due to the chemical complexity of the mo-
lecules it is difficult to determine the anticorrosive mechanism involved
in the microemulsion actuation.
Surfactants and cosurfactants (surfactants with small lipophilic
chain) have proven anti-corrosive activity for the protection of metallic
materials against corrosion. The amphiphilic nature of surfactant mo-
lecules creates an affinity for adsorption at interfaces such as metal/
metal oxide–water interface. The polar head of the surfactant can in-
teract with the metal surface with a hydrocarbon tail directed towards
the aqueous medium, forming a successive layer with the ability to
isolate/reduce the contact between the steel surface and the aggressive
medium, thus increasing the inhibition effectiveness [42]. The micelles
formed by the surfactants and cosurfactants in the microemulsion can
adsorb onto the metal surface and form a protective film against cor-
rosion. Depending on the organization of these molecules, the interac-
tion between them can cause the formation of layers increasing the
thickness of the film
formed, intensifying the protection of the metal [15,42,43].
Passion fruit seed oil is composed of unsaturated fatty acids, in-
cluding mainly linoleic, palmitic, myristic and stearic acids, as well as
tocopherol and phenolic compounds [16–18]. Some of these chemical
structures are disposed in Fig. 12. It can be observed that all the com-
pounds present polar groups in their chains, such as linoleic acid, and
A.V. Souza, et al.
Fig. 8. (a) and (b) Stimulated circuit fitted to the obtained EIS data; b) Circuit used to fit the experimental EIS data of blank at T = 60 °C.
also unsaturated, heteroatoms and aromatic rings, as in tocopherols.
These groups allow interactions with the metal surface through pi
bonding and Van der Waals bonds, adsorbing on the metal surface to
form a protective film.
All the components of the microemulsion have in their structure
elements that enable interaction with the metal surface. Because of this,
it’s possible suggest that the microemulsion system has acted in dif-
ferent ways in a synergetic form, resulting in good protection effects of
the carbon steel surface. The results of the polarization and impedance
curves show that the system acted like an adsorption inhibitor and the
11
Colloids and Surfaces A 599 (2020) 124934
SEM images clearly show the capacity of the inhibitor to form a pro-
tective film on the steel surface.
It must be highlighted that discussion of the adsorption isotherm
behavior using green extracts as inhibitors in terms of thermodynamic
parameters, such as the standard free energy of adsorption value
(ΔGads), is not possible because the molecular mass of the component
responsible for adsorption process is not known. There are a several
compounds in the passion fruit seed oil that can act as corrosion in-
hibitor. This limitation is common to studies using extracts of natural
products as corrosion inhibitors, and was previously reported
A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Table 8
Electrochemical parameters of EIS tests.
Rs (Ω. cm2) Rct (Ω. cm2) Y0 (CPE) (Sn Ω−1. cm−2) n (0 < n < 1) Cdl (μF/cm2) fmax (Hz) Fit error (Chi-squared) IE (%)

25 °C
blank 5.10 166.40 3.3 10−4 0.872 236.9 2.12 0.0061 –
0.5 % 7.13 800.80 2.4 10−5 0.903 16.71 6.55 0.0039 79.22
1% 7.50 857.70 1.6 10−5 0.821 8.44 5.72 0.0063 80.21
1.5 % 841 2103.42 9,6 10−6 0.993 9.35 6.12 0.0042 92.08
40 °C
blank 4.38 81.99 3.3 10−4 0.991 340.20 3.72 0.0075 –
0.5 % 3.39 521.20 2.4 10−5 0889 28.41 6.55 00,014 84.26
1% 4.31 973.40 1.6 10−5 0.725 9.02 8.68 0.0029 91.57
1.5 % 4.21 988.11 9,6 10−6 0.901 173 6.55 0.0052 9170
60 °C
Blank 3.01 53.73 9.2 10−4 0.761 404.81 4.94 0.0045 –
0.5 % 2.33 214.60 2.7 10−4 0.811 173.01 6.55 0.0019 74.96
1% 3.70 245.20 1.7 10−4 0.804 77.63 8.68 0.0036 78.08
1.5 % 4.01 400.30 9.5 10 −5 0.828 47.72 8.68 0.0070 86.50

[7,45,47–49]. average droplet sizes between 22.5 and 75.0 nm. Among the mi-
croemulsions prepared, M6 and M8 were selected for corrosion
4. Conclusions studies due to their greater stability and monodispersed droplet
distribution.
1 The microemulsions obtained were of the water-in-oil type and had 2 The results of the gravimetric tests showed that, in general,

Fig. 9. Polarization curves for API P110 carbon steel in brine saturated with CO2 in the presence and absence of microemulsion M8: (a) 25 °C; (b) 40 °C and (c) 60 °C.

12
A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

Table 9
Electrochemical parameters of polarization tests.a
Icorr (μA/ -Ecorr (mVAg/ ba (mV/ bc (mV/ CR (mm/ IE (%)
cm2) Agcl) dec) dec) y)

25 °C
blank 533 680.85 36.62 61.79 1.188 –
0.5 % 12.7 617.00 32.10 78.80 0.147 97.62
1% 9.66 635.38 34.30 80.10 0.112 98.19
1.5 % 4.93 604.00 41.30 80.20 0.057 99.07
40 °C
blank 144 672.30 42.90 97.40 1.672 –
0.5 % 9.4 629.88 32.5 54.9 0.109 93.48
1% 8.76 624.54 32.0 48.0 0.102 93.89
1.5 % 7.6 625.12 32.10 34.40 0.089 94.67
60 °C
Blank 262 678.20 51.30 100.7 3.042 –
0.5 % 75.2 635.70 43.50 98.40 0.873 71.30
1% 39.4 649.90 47.10 41.20 0.457 84.97 Fig. 11. Contact angle measurements in the presence and absence of corrosion
1.5 % 18 634.77 20.70 71.00 0.209 93.13 inhibitor M8.

a
Values obtained by duplicate tests.
the inhibitor, characterizing the inhibition action as mixed or by
adsorption.
microemulsion M8 was more efficient than M6, even with variations
5 The SEM images and contact angle values indicated that the pre-
of temperature and inhibitor concentration, reaching, maximum
sence of the microemulsion M8 caused formation of an adsorbent
efficiency of 97.5 % at 25 °C.
film, promoting protection of the metal surface.
3 The OCP, LPR, EIS and potentiodynamic polarization studies
6 Overall, the results of this work showed that the development of the
showed that the microemulsions M8 can provide a inhibition effi-
corrosion inhibitor formulation composed by microemulsion based
ciency up to 99 % for carbon steel P110 in synthetic brine saturated
on the surfactant and passion fruit seed oil presented IE values near
with CO2. These results are in agreement, suggesting that the three
100 % with only 1.5 % (v/v) of the inhibitor. Therefore, the mi-
independent techniques confirm the validity of the results.
croemulsion M8 analyzed has good potential for application as an
4 The anodic and cathodic polarization curves showed shifts to lower
eco-friendly corrosion inhibitor, produced from a plentiful renew-
current density values, indicating the formation of a film on the
able resource, for use to protect metal surfaces at low cost and with
metal surface. In contrast, the Ecorr value was not altered by adding

Fig. 10. SEM micrographs of the test coupons of API P110 carbon steel: (a) polished; (b) blank T = 25 °C; (c) blank T = 40 °C; (d) blank T = 60 °C; (e) with M8
T = 25 °C; (f) with M8 T = 40 °C; (g) with M8 T = 60 °C.

13
A.V. Souza, et al. Colloids and Surfaces A 599 (2020) 124934

[8] A. Dehghani, G. Bahlakeh, B. Ramezanzadeh, J. Mol. Liq. 282 (2019) 366–384.

[9] M. Mobin, M. Rizvi, Carbohydr. Polym. 160 (2017) 172–183.
[10] K. Anupama, A. Joseph, Journal of Bio-and Tribo-Corrosion. 4 (2018) 1–14.
[11] J. Stephen, A. Adebayo, J. Fail. Anal. Prev. 18 (2018) 350–355.
[12] L.B. Furtado, R.C. Nascimento, P.R. Seidl, M.J.O.C. Guimarães, L.M. Costa,
J.C. Rocha, J.A.C. Ponciano. J. Mol Liq. 284 (2019) 393–404.
[13] M. Mobin, M. Rizvi, Carbohydr. Polym. 156 (2017) 202–214.
[14] N.K. Gupta, P.G. Joshia, V. Srivastava, M.A. Quraishi, Int. J. Biol. Macromol. 106
(2018) 704–711.
[15] E.F. Moura, A.O.W. Neto, T.N.C. Dantas, H.S. Júnior, A. Gurgel, Colloids Surf. A 340
(2009) 199–207.
[16] M.A.R. Vieira, C.R.L. Carvalho, Soares-Scott, L.M. Melleti, J.P.F. Teixeira,
L.A. Ambrósio, M.O.M. Marques, 46º Congresso Brasileiro de Olericultura, (2006).
[17] A. Ferrari, F. Colussi, R.A. Ayub, Rev. Bras. Frutic. 26 (2004).
[18] N. Jorge, C.R. Malacrida, P.M. Angelo, D. Andreo, Pesq. Agropec. Trop. 39 (2009)
380–385.
[19] P.B. Raja, M.G. Sethuraman, Mater. Lett. 62 (2008) 113–116.
[20] G.C. Anjos, Utilização de matérias primas vegetais para aplicabilidade como cor-
rosion inhibitors, Dissertação de mestrado. Programa de pós-graduação em ciências
e engenharia de metais, Universidade Federal do Rio Grande do Norte, Natal, 2012.
[21] S.M.W. Zanin, M.D. Miguel, M.C. Chimelli, A.B. Oliveira, Visão Acadêmica Curitiba
3 (2002) 3–8.
Fig. 12. Chemical structures of linoleic acid and tocopherol present in passion [22] A. Kalaitzaki, M. Poulopoulou, A. Xenakis, V. Papadimitriou, Colloids Surf. A:
fruit seed oil. Physicochem. Eng. Asp. 442 (2014) 80–87.
[23] R.T.R. Carvalho, P.F. Oliveira, L.C.M. Palermo, A.A.G. Ferreira, C.R.E. Mansur, Fuel
238 (2019) 75–85.
low toxicity. [24] A.T. Tyowua, S.G. Yiase, B.P. Binks, J. Colloid Interface Sci. 488 (2017) 127–134.
[25] H. Cen, Z. Chen, X. Guo, J. Taiwan Inst. Chem. Eng. 99 (2019) 224–238.
[26] C.P. Fernandes, M.P. Mascarenhas, F.M. Zibetti, B.L. Lima, P.R.F. Oliveira, L. Rocha,
CRediT authorship contribution statement
J. Braz, Pharmacognosy 23 (2013) 108–114.
[27] P.A. Winsor, Trans. Faraday Soc. 46 (1950) 762–772.
Aline V. Souza: Data curation, Writing - original draft. Janaína C. [28] I.C.V.M. Santos, R.R. Martelloti, P.F. Oliveira, C.R.E. Mansur, Fuel 210 (2017)
da Rocha: Visualization, Investigation. J.A.C. Ponciano Gomes: 684–694.
[29] V. Gentil, Corrosion, LTC, 6°. ed. LTC, Rio de Janeiro, 2011.
Supervision. Luiz C.M. Palermo: Conceptualization, Methodology, [30] X. Jiang, Y.G. Zheng, W. Ke, Corros. Sci. 47 (2005) 2636–2658.
Software. Claudia R.E. Mansur: Writing - review & editing. [31] F. Farelas, A. Ramirez, Int. J. Electrochem. Sci. 5 (2010) 797–814.
[32] A.B. da Silva, J.A.C.P. Gomes, E. D’Elia, M.J.C. Rezende, A.C. Pinto, B.N.M. Silva,
B.V. Silva, Int. J. Electrochem. Sci. 8 (2013) 9317–9331.
Declaration of Competing Interest [33] Z. Chen, X. Guo, Inhibition J. Electrochem. Soc. 164 (2017) 602–609.
[34] M.V. Azghandi, A. Davoodi, G.A. Farzi, A. Kosari, Corros. Sci. 64 (2012) 44–54.
[35] X. Luo, X. Pan, S. Yuan, S. Du, C. Zhang, Y. Liu, Corros. Sci. 125 (2017) 139–151.
The authors declare that they have no known competing financial [36] H. Bentrah, Y. Rahali, A. Chala, Corros. Sci. 82 (2014) 426–431.
interests or personal relationships that could have appeared to influ- [37] L.L. Shreir, R.A. Jarman, G.T. Burstein, Corrosion Volume 2- Corrosion Control, 3rd
ence the work reported in this paper. ed., Butterworth-Heinermann, 1994.
[38] R.C. Nascimento, L.B. Furtado, Maria José O.C. Guimarães, Peter R. Seid,
J.C. Rocha, J.A.C. Ponciano, M.T.M. Cruz, J. Mol. Liq. 256 (2018) 548.
Acknowledgments [39] E. McCafferty, Corros. Sci. 47 (2005) 3202.
[40] S.A. Umoren, A.A. AlAhmary, Z.M. Gasem, M.M. Solomon, Int. J. Biol. Macromol.
117 (2018) 1017–1028.
We thank CAPES, CNPq, Faperj and Petrobras for financial support.
[41] S.A. Umoren, Y. Li, F.H. Wang, Corros. Sci. 52 (2010) 2422–2429.
[42] Y. Zhu, M.L. Free, R. Woollam, W. Durnie, Prog. Mater. Sci. 90 (2017) 159–223.
References [43] A.O.W. Neto, E.F.M, H.S. Júnior, T.N.C. Dantas, A.A.D. Neto, A. Gurgel, Colloids
Surf. A: Physicochem. Eng. Asp. 398 (2012) 76–83.
[44] L.L. Liao, S. Mo, H.Q. Luo, N.B. Li, J. Colloid Interface Sci. 520 (2018) 41–49.
[1] H. Zhang, K. Gao, L. Yan, X. Pang, J. Electroanal.Chem. 791 (2017) 83–94. [45] V.V. Torres, R.S. Amado, C.F. Sá, T.L. Fernandez, C.A.S. Riehl, A.G. Torres,
[2] B.J. Usman, S.A. Umoren, Z.M. Gasem, J. Mol. Liq. 237 (2017) 146–156. E. D’Elia, Corros. Sci. 53 (2011) 2385.
[3] B.D.B. Tiu, R.C. Advincula, React. Funct. Polym. 95 (2015) 25–45. [46] I.B. Obot, I.B. Onyeachu, A.M. Kumar, Carbohydr. Polym. 178 (2017) 200–208.
[4] S. Nešić, Corros. Sci. 49 (2007) 4308–4338. [47] L. Valek, S. Martinez, Mater. Lett. 61 (2007) 148.
[5] M. Goyal, S. Kumar, I. Bahadur, C. Verma, E. E, J. Mol. Liq. 256 (2018) 565–573. [48] J.C. Rocha, J.A.C.P. Gomes, E. D’Elia, Mater. Res. 17 (6) (2014) 1581–1587.
[6] T. Rabizadeh, S. Khameneh Asl, J. Mol. Liq. 276 (2019) 694–704. [49] M. Lebrini, F. Robert, A. Lecante, C. Roos, Corros. Sci. 53 (2011) 687.
[7] J.C. da Rocha, J.A.C.P. Gomes, E. D’Elia, Corros. Sci. 52 (2010) 2341–2348.

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