Industrial Crops & Products 119 (2018) 111–124

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Industrial Crops & Products

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

Development and evaluation of a green corrosion inhibitor based on rice T

bran oil obtained from agro-industrial waste
⁎
G. Salinas-Solanoa,b, , J. Porcayo-Calderonc, L.M. Martinez de la Escalerad, J. Cantod,
M. Casales-Diazb, O. Sotelo-Mazonb, John Henaoe, L. Martinez-Gomeza,b,c
a
Instituto de Física, Circuito de la Investigación Científica s/n, Ciudad Universitaria, 04510, México
b
Instituto de Ciencias Físicas, Universidad Nacional Autónoma de México, Avenida Universidad s/n, 62210 Cuernavaca, Mor., México
c
CIICAp, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, 62209 Cuernavaca, Mor., Mexico
d
Corrosión y Protección (CyP), Buffon 46, 11590 México City, DF, México
e
CONACyT-CIATEQ A.C., Parque Industrial Bernardo Quintana, Av. Manantiales 23A, El Marqués, Querétaro, C.P.76246, México

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

Keywords: In this study, agro-industrial waste was used to prepare a green corrosion inhibitor based on rice bran oil. Firstly,
Agro-industrial waste the rice-bran oil was recovered and filtered, and then a semi-refined process was applied to separate the waxes.
Corrosion The performance of the synthetized inhibitor was evaluated on a 1018 steel surface by means of different
Rice bran oil electrochemical techniques such as potentiodynamic polarization, open circuit, linear polarization resistance
Green inhibitor
and electrochemical impedance spectroscopy (EIS). The present results have shown that the addition of 10 and
Imidazoline
25 ppm of inhibitor improves the performance of the system, presenting efficiencies above 99%. Interestingly,
O
the free-energy calculated for the rice bran oil (ΔGads = −53.80 kJ/mol) pointed out the good affinity of the
inhibitor with respect to the steel surface. Moreover, the EIS spectra showed the formation of a protective layer
caused by the adsorption of the inhibitor on the steel surface. This layer improved remarkably the charge-
transfer resistance of the metallic material.

1. Introduction
Corrosion resistance of carbon steels is an issue that often affects the
oil and gas industries, being the source of great economic losses. For
instance, carbon steel pipes are usually corroded by CO2 and their
failure often leads to enormous losses of oil (Okafor et al., 2009). The
use of additives, namely “corrosion inhibitors”, has been proposed as a
solution to this problem. Inhibitors are substances that are added in
small concentrations (part per million, ppm) into the corrosive media to
prevent corrosion reactions. Previous studies have reported that organic
compounds containing N, S and O, can reduce dramatically the corro-
sion rate of metallic components. However, most of these compounds
are expensive and toxic (Raja and Sethuraman, 2008).
Natural products such as vegetable oils have gained enormous at-
tention of specialists within the corrosion industry since these type of
products can be used for the preparation of a new generation of in-
hibitors, namely “green corrosion inhibitors” (Yoo et al., 2012). These
type of inhibitors are potentially cheaper and safer than conventional
ones. Among various natural products, the rice oil is regarded as a
promising precursor for the preparation of green inhibitors. Rice oil is
often extracted from rice bran (cuticle) which is a by-product obtained
during the rice grain bleaching process and contains around 15–23% of
rice oil (Amarasinghe and Gangodavilage, 2004; Frank and Gunstone,
2004; Ju and Vali, 2005).
The most widely used inhibitors in gas and oil industry are imida-
zoline derivatives. These type of inhbitors are obtained from amides,
however, recent studies have shown that imidazoline derivatives can be
also produced from natural oils (Chen et al., 2000; Ortega-Toledo et al.,
2011; Wang et al., 1999; Jovancicevic et al., 1999; Porcayo-Calderon
et al., 2015a,b). Overall, the synthesis of these compounds involves the
dehydration reaction between aminoethylethanolamine and fatty acids
at high temperatures (Martinez-Palou et al., 2003). In previous litera-
ture, some green corrosion inhibitors have been reported. For instance,
the hydroxietilimidazoline derivative prepared from coffee oil was
evaluated onto carbon steel within a solution containing 3%
NaCl + 10% diesel and CO2 at 50 °C. Interestingly, the green imidazo-
line derivative had a good performance as inhibitor, presenting a de-
crease of the corrosion rate up to 99% with a concentration of 10 ppm
(Porcayo-Calderon et al., 2015a,b). The 2-undecil-1-aminoethyl imi-
dazoline (AEI-11) and 2 undecil-1-aminoethyl-1-hidroxietil quaternary

⁎
Corresponding author at: Instituto de Física, Circuito de la Investigación Científica s/n, Ciudad Universitaria, 04510, México.
E-mail addresses: salinas_solanoguillermo@hotmail.com (G. Salinas-Solano), canto@nacemexico.org (J. Canto), mcasales@icf.unam.mx (M. Casales-Diaz),
osotelo@icf.unam.mx (O. Sotelo-Mazon).

https://doi.org/10.1016/j.indcrop.2018.04.009
Received 16 December 2017; Received in revised form 28 March 2018; Accepted 2 April 2018
Available online 11 April 2018
0926-6690/ © 2018 Elsevier B.V. All rights reserved.
G. Salinas-Solano et al.
imidazoline (AQI-11) have been also studied as inhibitors. These
compounds were evaluated onto N80 mild steel, both presenting a good
performance as CO2 corrosion inhibitors (Liu et al., 2009).
Due to the growing interest on green corrosion inhibitors and their
reported remarkable performance, the present study is focused on the
synthesis of an imidazoline-based corrosion inhibitor from semi-refined
rice bran oil (agro-industrial waste). The inhibitory performance of the
imidazoline-based compound as corrosion inhibitor for 1018 carbon
steel in CO2 saturated aqueous solution was investigated by means of
potentiodynamic polarization, linear polarization resistance, open cir-
cuit measurements and EIS. Optical microscopy was employed to ana-
lyze the protection behavior of the inhibitor on the surface of the 1018
carbon steel.
2. Experimental procedure
2.1. Synthesis of the rice bran oil-based inhibitor
Rice bran from a local variety “Arroz Morelos” (Puente de Ixtla,
Morelos, MEXICO) was used as a raw material for the preparation of the
inhibitor. The Soxhlet method was employed to extract the crude oil
using hexane as a solvent. Afterwards, a bleaching process was carried
out on the crude oil using 2% Tonsil and 0.5% activated carbon (%wt
on oil). This process was performed at 95 °C and under constant stirring
for 20 min. The oil obtained was filtered under a suction method (De
and Bhattacharyya, 1998), and mixed with water at 95 °C. Finally, the
obtained emulsion was centrifuged (Thengumpillil Narayana et al.,
2002) to obtain the semi-refined rice bran oil. This semi-refined oil was
the precursor solution in the synthesis of the imidazoline-based in-
hibitor.
The inhibitor synthesis process was carried out in two stages as il-
lustrated in Fig. 1. In the first step, the direct amidation reaction of oil
and hydroxyethyl ethylene diamine was performed at 140 °C for 2.5 h.
This reaction was monitored by means of the thin layer chromato-
graphy technique (TLC) using heptane-ethyl acetate (9:1) as eluent. The
reaction products were removed by washing and filtering and were
analyzed using the Fourier transform infrared spectroscopy technique
(FTIR) (Lee et al., 2007; Porcayo-Calderon et al., 2017; Reyes-Dorantes
et al., 2017). The second synthesis step consisted on performing the
imidazoline cyclization reaction. This reaction was achieved after
heating the purified fatty-amide under vacuum conditions (23.5 in Hg)
at 160 °C for 16 h (Bistline et al., 1983; Bajpai and Tyagi, 2006; Yoo
et al., 2012). The imidazoline cyclization reaction was monitored by
means of TLC using (8.5:1.5:5) dichloromethane, methanol, ammonium
hydroxide as eluent while the reaction products were analyzed using
FTIR and 1H NMR.
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Industrial Crops & Products 119 (2018) 111–124
2.2. Electrochemical performance
The electrochemical performance of the inhibitor was evaluated in a
conventional three-electrode cell. A mixture of brine (3% NaCl) and
diesel (90:10) (% vol.) was used as electrolyte; meanwhile, a 1018 mild
steel (25 mm longitude × 5 mm diameter), a platinum wire and a gra-
phite bar were selected as working, reference and counter electrodes,
respectively. In addition, the electrolyte was saturated with CO2, which
was introduced into the cell 15 min before starting the electrochemical
corrosion tests and was kept for 24 h. Various amounts of inhibitor were
intentionally added to the electrolyte after one hour of open circuit
condition. The amounts of inhibitor added were 0.0, 2.5, 5.0, 10.0,
25.0, 50.0 and 100.0 ppm.
The corrosion behavior of the working electrode, for each single
inhibitor addition, was monitored by means of potentiodynamic po-
larization (PP), linear polarization resistance (LPR), open circuit po-
tential (OCP) and electrochemical impedance spectroscopy (EIS). The
PP technique was carried out at 1 mV/s from −1000 mV to 200 mV vs
Ecorr. LPR measurements were performed from −20 to 20 mV vs OCP at
1 mV/s. AC signals were applied in the EIS measurements with 10 mV
amplitude and with a frequency range from 100 kHz to 10 mHz
(González-Rodríguez et al., 2016). These electrochemical studies were
carried out using a Gamry Interface 1000 Potentiostat/Galvanostat/
ZRA analyzer.
3. Results and discussion
3.1. Rice bran oil-based inhibitor
Fig. 2 shows the FTIR analysis carried out on the semi-refined rice
bran oil inhibitor. One can observe the bands corresponding to the main
functional groups of the oil. The band located at 3007 cm−1 is related to
the symmetrical vibrations of the alkenes ]CeH that appear in the
long chains of the oils. At wavelengths values of 2922 and 2853 cm−1,
the bands are related to asymmetric and symmetrical vibrations of CeH
extensions of lipids (Dreissig et al., 2009). At 1743 cm−1, a band related
to the carbonyl ester group C]O, typical of triglycerides, is observed.
At low frequencies, centered bands assigned to CH groups are also
observed. Bands corresponding to the CH3 group appear at 1375 cm−1
with symmetrical bending vibration. At 1161 cm−1, the bands asso-
ciated with the CO group are also observed. At 721 cm−1, a centered
band appears due to the vibrational superposition of the eHC]CHe
group of the cis-disubstituted olefins (flexion vibration) and the sym-
metrical vibration of the methylene (Lukas et al., 1997; Rohman and
Che Man, 2012).
The imidazoline inhibitor was obtained by means of a synthesis
process involving an aminolysis reaction of its precursor. During the
synthesis, the semi-refined rice bran oil reacts directly with the N-(2-
hydroxyethyl) amino ethylamine, requiring a purification process to
Fig. 1. Synthesis of the imidazoline-based in-
hibitor from semi-refined rice bran oil, (1) N-
(2-hydroxyethyl) amino ethylamine, (2) Rice
bran oil, (3) N- [2 − [(2- hydroxyethyl) amino]
ethyl] −amide, Fatty amide, and (4) Fatty-
Imidazoline derivatives from de raw rice bran
oil, where R = alkyl chains of the rice bran oil
fatty acids.
G. Salinas-Solano et al.
Fig. 2. FTIR spectrum of the semi-refined rice bran oil.
Fig. 3. FTIR spectrum for the crude fatty-amide and purified fatty-amide.
remove by-products. In Fig. 3, FTIR spectra show that both crude fatty-
amide and purified fatty-amide have similar bands, with the largest one
corresponding to the amides group. However, the FTIR spectrum of the
purified fatty-amide presents the largest amide bands in the wavelength
range from 1642 to 719 cm−1. Both FTIR spectra show a broad band
around 3296 cm−1 corresponding to the NH group from a secondary
amide. It also shows the presence of a very acute band around
1642 cm−1 corresponding to the C]O group, and a band at
1552.83 cm−1 corresponding to the vibration of the NH group, which is
followed by a broad band at 1461.58 cm−1 associated with the CN
group of the amide. The presence of two sharp and strong bands at
2921.17 and 2852.08 cm−1 is related to the groups eCH3 and ]CH2,
respectively. The band located at 3008.22 cm−1 is given by the sym-
metrical vibrations of the alkenes ]CeH with long chains.
In Fig. 4, the FTIR spectrum of the fatty-imidazoline shows a strong
band with an acute peak 1605.17 cm−1 corresponding to the C]N
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Industrial Crops & Products 119 (2018) 111–124
group of the imidazolines. The band located at 1646.92 cm−1 is related
to the group C]O. In a similar way, at frequency values of
1550.40 cm−1, the vibration of the NeH group is observed. The two
large bands at 2921.83 and 2852.39 cm−1 correspond to the groups
−CH3 and ]CH2, respectively. The band located at 3007.31 cm−1 is
related to the double bonds (]CeH) that are present in the hydro-
carbon chains of the rice oil (Martin and Valone, 1985).
Fig. 5 shows the 1H NMR (300 mHz, CD3OD) spectrum of the imi-
dazoline derivatives obtained from rice bran oil. This spectrum shows
two peaks at δ 3.7 ppm and δ 3.26 ppm that can be associated with
protons located within the imidazoline ring (m, eCH2, 4H). The peaks
observed at δ 3.6 y δ 3.3 ppm are linked to the protons in the pendant
group (m, eCH2, 4H). Moreover, the peaks at δ 2.1 and δ 1.59 ppm also
show the protons of (m, eCH2, 4H) group, while the peaks at δ 5.3 and
δ 1.28 ppm show the protons of the alkyl chain group of fatty acids (m,
eCH]CHe, 2H). Finally, the peak at δ 0.92 ppm is associated with the
G. Salinas-Solano et al.
Fig. 4. FTIR spectrum of the imidazoline obtained from the rice bran oil.
(CH3) group (Yoo et al., 2012; Zhang et al., 2015).
3.2. Potentiodynamic polarization curves
Fig. 6 shows the effect of different concentrations of inhibitor on the
potentiodynamic polarization curves of the 1018 carbon steel. It can be
noticed that the polarization curve without inhibitor has an active be-
havior in the anodic branch. This is related to the rapid dissolution of
the corrosion products that act on the steel surface to protect against
corrosive species. Moreover, the Ecorr value observed on the polariza-
tion curve, without adding the inhibitor, is the noblest one in com-
parison to those obtained when the inhibitor is added. However, the
corrosion rate at 0 ppm of inhibitor is the biggest, resulting in a largest
corrosion density among all the concentrations studied. On the other
hand, once the inhibitor is added, an increase in the slope of the anodic
branches and a decrease in the Icorr values is observed. Certainly, this
fact is the result of the protective effect of the inhibitor, which formed a
protective film onto the carbon steel surface that prevented the diffu-
sion of ions towards the surface of the material. The polarization curves
also show that the Ecorr of the 1018 steel is shifted towards more active
positions when compared to the Ecorr without inhibitor, implying that
Fig. 5. 1H NMR (300 mHz, CD3OD) spectrum for the imidazoline derivatives obtained from the rice brain oil.
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Industrial Crops & Products 119 (2018) 111–124
the inhibitor acts as a cathodic type one (Ali et al., 2008).
A summary of the electrochemical parameters obtained from the
polarization curves is presented in Table 1. One can observe that there
is a decrease towards more active corrosion potential values with the
addition of the inhibitor. Herein, the most negative value was obtained
with the addition of 10 ppm. Furthermore, the highest corrosion density
value (0.057 mA/cm2) was obtained without the addition of the in-
hibitor, while the lowest Icorr value was 0.000234 mA/cm2 corre-
sponding to 5 ppm of inhibitor. Recent studies indicate that the increase
in the Icorr value with the increase in the concentration of the inhibitor
can be related to electrostatic forces of repulsion between the inhibitor
molecules and their packing on the surface of the metal. Consequently,
the Icorr values can increase when unprotected sites are created on the
metallic surface by either a low concentration or a concentration in
excess of the inhibitor. In particular, for excess of inhibitor, the elec-
trostatic repulsion forces prevent an efficient packing, causing the in-
hibitor desorption. This fact produces unprotected sites that are prone
to be corroded and leads to the increase in the Icorr values. (Porcayo-
Calderon et al., 2015a, 2015b; Rivera-Grau et al., 2012). On the other
hand, the inhibitor adsorbed on the metallic surface promotes a de-
crease in the corrosion potential values towards more active values,
G. Salinas-Solano et al. Industrial Crops & Products 119 (2018) 111–124

Fig. 6. Potentiodynamic polarization curves for 1018 steel at 50 °C and after 24 h of immersion. The different curves are the result of the tests performed with various
amounts of inhibitor added to the electrolyte.

Table 1 Fig. 8 shows that the OCP value of the system without inhibitor and
Electrochemical parameters obtained from polarization curves at 50 °C. with 5 ppm had a big fluctuation during the first 4 h of experiment,
ppm Ecorr (mV) Ba (mV/decade) Bc (mV/decade) Icorr (mA/cm2) which is associated with the rapid formation and dissolution of a film
on the metal surface. Afterwards, OCP values are quasi-stable. This fact
0 −479 1.23E + 02 1.87E + 02 5.78E-02 is related to the formation of stable corrosion products, building up a
2.5 −514 1.64E + 02 1.97E + 02 2.30E-02 thicker film with time. Alternatively, the other OCP values present the
5 −555 5.25E + 01 1.38E + 02 2.34E-04
10 −878 7.16E + 01 2.83E + 02 5.84E-04
fluctuation during the first 2 h of experiment. Herein, the rapid drop in
25 −788 1.03E + 02 6.14E + 02 4.32E-04 potential is related to the adsorbed inhibitor on the surface of the 1018
50 −621 5.47E + 01 4.24E + 02 1.55E-03 carbon steel. Porcayo-Calderon et al. indicate that a rapid drop in po-
100 −743 5.82E + 01 3.18E + 02 2.55E-04 tential values may be associated with the addition of the inhibitor to the
corrosive medium, leading to a change in the chemical equilibrium of
the corrosive system because of the addition of an alkaline compound
which is caused by the effect of blocking the active sites (Cao, 1996;
(Porcayo-Calderon et al., 2017). Other researchers indicate that OCP
Jiang et al., 2005a). This fact is associated with changes in the average
values indicating more activity may be related to the type of inhibitor
values of energy barriers for the activation of the cathodic and anodic
used (Li et al., 2008; Heydari and Javidi, 2012). When the difference in
reactions. Furthermore, the inhibition effect depends not only on the
OCP values is at least 85 mV in relation to the potential measured for
inhibitor, but also on the anion in the solution (Cao, 1996; Lorenz,
the test without inhibitor, corrosion inhibitors can be classified as
1986). In fact, the density of active sites changes with the addition of
anodic or cathodic type or mixed type (Amin et al., 2011; Al-Otaibi
the inhibitor that promotes also a change in the Ecorr and in the anodic
et al., 2014). According to the previous observations and the OCP re-
and cathodic reactions rate (Farelas and Ramirez, 2010).
sults obtained, the inhibitor obtained in the present study could be
The effect of the inhibitor concentration on the corrosion potential
classified as a cathodic type inhibitor. In addition, the most active
(Ecorr) and corrosion current density (Icorr) is presented in Fig. 7. One
corrosion potential values were observed with the addition of 10 ppm
can observe a decrease of both Ecorr and Icorr values with the increment
followed by OCP values of 25 and 100 ppm.
of the inhibitor concentration. The highest corrosion rate was obtained
without the inhibitor addition. One can also observe that Icorr values
3.4. Linear polarization resistance measurements
decrease and remain quasi-constant with the addition of inhibitor
amounts superior to 5 ppm.
Fig. 9 shows the values of RPL for the 1018 carbon steel as a
function of the inhibitor concentration. The values of Rp were obtained
3.3. Open circuit potential measurements by polarizing the working electrode with ± 20 mV with respect to the
OCP value (Porcayo-Calderon et al., 2017). The Rp values without in-
Fig. 8 shows the effect of different concentrations of inhibitor on the hibitor show big fluctuations during the first 7 h due to the formation
open circuit potential for the 1018 carbon steel. It is well known that by and dissolution of the corrosion products. Afterwards, the Rp value
monitoring the open circuit potential, the formation of protective cor- remained stable throughout the test. When the inhibitor concentration
rosion products can be evaluated. According to Gurappa et al. an in- was increased, the polarization resistance values also increased. This
crease in potential values in the positive direction indicates the for- fact indicates that the addition of the inhibitor had an inhibitory effect
mation of a passive film related to corrosion products, while a stable since it decreased the corrosion rate of the material. The results also
potential indicates that the film is stable and protects the surface. show that the best corrosion resistance was presented for 10 and
Moreover, a drop of potential towards negative values suggests 25 ppm, respectively, and the lowest corrosion resistance was observed
breakage, dissolution and/or non-formation of this film (Gurappa, with addition of 50 ppm. The decrease in the Rp value with the increase
2002). in the concentration of the inhibitor is related to the packing efficiency

115
G. Salinas-Solano et al.
Fig. 7. Effect of the imidazoline inhibitor on the electrochemical parameters obtained from the polarization curves at 50 °C.
of the molecules on the metal surface and the electrostatic repulsive
forces between them. If the concentration of the inhibitor is low, un-
protected active sites are still present on the surface. However, when
there is an excess of inhibitor, electrostatic repulsion forces can prevent
an efficient packing and, as a result, active sites can appear on the
surface. (Porcayo-Calderon et al., 2015a,b; Rivera-Grau et al., 2012).
Consequently, in this study, the addition of high doses of inhibitor led
to increase the density of active sites, which led to increase the corro-
sion rate and to decrease the Rp value. On the other hand, the decrease
in the Rp value at high concentrations is related to the adsorption mode
of the inhibitor. At low concentrations, the inhibitor molecules are
adsorbed vertically on the metal surface through either a single co-
ordinated iron-nitrogen bond or the interaction of a π-electron. When
the concentration the molecules is increased, these are absorbed in a
planar position by interacting with the two nitrogen atoms present in
Fig. 8. OCP curves for 1018 carbon steel at 50 °C as a function of time and inhibitor concentration.
116
Industrial Crops & Products 119 (2018) 111–124
the inhibitor (Hackerman et al., 1975; Durnie et al., 1999). In this
manner, when 10 and 25 ppm of inhibitor was used, the adsorption of
the molecules can be assumed that was flat, reaching the highest Rp
values and the best corrosion efficiencies. However, when the con-
centration was increased, the molecules repelled each other, so that the
inhibitor molecules tended to adsorb perpendicularly on the metal
surface due to the electrostatic repelling function that occupies a small
area on the metal surface (Jiang et al., 2005b). Therefore, at high
concentrations of the inhibitor, the corrosion rates increased markedly.
The inhibition efficiency of the rice bran oil-based imidazoline is
shown in Fig. 10. The efficiency values were calculated from experi-
mental RPL values according to the following equation:
R c , i − Rs , i
E (%) =
R c, i (1)
G. Salinas-Solano et al. Industrial Crops & Products 119 (2018) 111–124

Fig. 9. RPL curves for 1018 carbon steel at 50 °C as a function of time and inhibitor concentration.

Where: Rs,i = LPR without inhibitor, Rc,i = LPR with inhibitor. The re- corrosion test are used. The efficiency of the inhibitor (E%) is directly
sults show that a rapid increase in the efficiency takes place im- related to the coated surface (θ) of the electrode by the corrosion in-
mediately after adding the inhibitor. Afterwards, stable efficiency va- hibitor, ie, E% = θ (Jawich et al., 2012; Zhanhg et al., 2001). The va-
lues are observed. The efficiencies achieved were in the range from lues (θ) of the percentage of the area covered by the inhibitor were
98.24 to 99.69%, where the best one (99.69%) corresponded to the determined by means of the RPL values at different concentrations (2.5,
addition of 10 ppm. Interestingly, these results indicate the effective- 5, 10, 25, 50 and 100) ppm. The adsorption of the inhibitor can be
ness of the inhibitor to reduce the corrosion of the steel surface. determined by the Langmuir equation:
θ
= K ads C
(1 − θ) (2)
3.5. Langmuir adsorption isotherm
Reordering Eq. (2):
The Langmuir isotherm is commonly used to determine the ad-
C 1
sorption of the inhibitor on the surface of the material which is sub- = +C
θ K ads (3)
jected to a determined corrosive environment. In the Langmuir model,
the values of θ (% of the working electrode surface covered by the in- Kads is the equilibrium constant of the adsorption process and is related
o
hibitor) and the concentration (mol/L) of the inhibitor in each to the adsorption free energy, ΔGads , by the following equation:

Fig. 10. Inhibition efficiency of the rice bran oil-based imidazoline synthesized.

117
G. Salinas-Solano et al.
Fig. 11. Langmuir adsorption isotherm of the inhibitor in 1018 carbon steel into corrosive electrolyte.
O hydrocarbons that act as a barrier against water and chlorides, and 3)
1 −ΔGads
K ads = exp ⎛⎜ ⎞⎟
55.5
⎝ RT ⎠
Getting finally:
ΔGO = −RTln (K ads *55.5)
Where, R = 8.314472 J/K-mol, T = 323.28 K. The values obtained by
C/θ vs C were plotted in Fig. 11, obtaining a straight line with a slope
close to the unit. This fact indicates that the adsorption process of the
inhibitor onto 1018 carbon steel surface follows the Langmiur adsorp-
tion isotherm. Langmuir isotherm is based on the absorption of the
inhibitor molecules by the displacement of the H2O molecules adsorbed
onto the metallic surface to form a film with protective characteristics
(Heydari and Javidi, 2012).
According to the experimental values, it was found that the re-
lationship between C vs C follows a linear trend, which can be ex-
θ
pressed according to equation 6. This trend had the same form as the
Langmuir equation (Eq. (3)).
C
= 1.0087C + 1.128x10−7
θ (6)
Where C is the concentration in mol/l and the value of the equilibrium
absorption constant Kads corresponds to the inverse of the ordinate to
1
the origin, K ads = 1.128x10−7 = 8865405.415. The absorption constant,
Kads, is related to the free standard energy of adsorption, ΔGads O
, using
O
Eq. (4) and (5). The calculated value of ΔGads was −53.80 kJ/mol. This
value indicates that the inhibitor adsorbs strongly on the surface of the
O suggests that the layers located on the surface of the material are not
material. It is well known that the values of ΔGads close to 20 kJ/mol are
associated with electrostatic interactions between the organic mole-
cules of the inhibitor and the surface of the material, which is known as
O it is possible to define the processes (diffusion and absorption) and
physisorption. Alternatively, the ΔGads values close to 40 kJ/mol are
related to strong interactions between the organic molecules of the
inhibitor and the metallic surface, which is known as chemisorption
(Heydari and Javidi, 2012, Dong et al., 2011). In the present study, the
O
ΔGads value obtained for the inhibitor indicates a high adsorption affi-
nity on the metal surface due to the sharing of charges between the
molecules and/or the formation of coordinated type bonds (chemi-
sorption). According to the report of Xueyuan Zhang et al., the high
inhibitory effect of imidazoline compounds is related to the structure of
the inhibitor. Especially, inhibition is caused by three factors, these are
1) nitrogen atoms located in the structural ring, 2) the long chain of
Industrial Crops & Products 119 (2018) 111–124
the unsaturated double bonds that are adsorbed chemically on the
(4)
surface of the Fe (which form a very stable protective film) (Zhanhg
et al., 2001).
(5)
3.6. Electrochemical impedance spectroscopy measurements
Fig. 12 shows the Nyquist and Bode diagrams for 1018 carbon steel
after 24 h immersion at 50 °C. One can note that the diagrams of Ny-
quist present a depressed capacitive semicircle whose diameter in-
creases when the inhibitor is added. Semi-circles of depressed appear-
ance, 0.5 ≤ n ≤ 1, are often associated with frequency dispersion
which is the result of either the inhomogeneity or surface roughness
(Hassan, 2007; Ashassi-Sorkhabi et al., 2008). Moreover, the increase in
the semi-circle diameter is commonly associated with an increase in the
charge transfer resistance, which is caused either by the formation of
protective corrosion products or by the process of adsorption of the
inhibitor, building up a protective film on the metallic surface that
isolates it from the corrosive environment (Solmaz et al., 2008). The
Nyquist diagram shows that the maximum diameter was obtained for
25 ppm of inhibitor.
The Bode diagrams shows various interesting characteristics. For
instance, in the absence of inhibitor, a typical response is observed and
is defined by the presence of a high frequency plateau (≥1000 Hz). It is
also observed a capacitive response of the working electrode surface at
intermediate frequencies, 1000 Hz > f < 1 Hz, which is characterized
by a slope less than −1 and a phase angle less than 90°. This fact
completely capacitive and/or protective (Amin et al., 2011; Porcayo-
Calderon et al., 2017). Moreover, in the low frequency region (< 1 Hz),
impedance occurring at the surface of the carbon steel. Interestingly,
the charge transfer resistance of the system without inhibitor is re-
markably lower than that measured with the inhibitor.
The impedance module format, |Z|, reveals that once the inhibitor is
added, two slopes less than −1 appear in the frequency range from high
to intermediate ones. These slopes are associated with two time con-
stants. The first time constant is observed at the high frequency region
due to the presence of the inhibitor on the metal surface (Porcayo-
Calderon et al., 2015a, 2015b), meanwhile the second time constant is
observed at intermediate frequency region due to the capacitive
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Fig. 12. Nyquist and Bode Diagrams for the 1018 carbon steel as a function of the inhibitor concentration. Data were collected during 24 h at 50 °C.

response of the carbon steel. On the other hand, one can observe an transfer resistance of the carbon steel, resulting in the reduction of the
increase in the impedance modulus, |Z|, at low frequencies when the corrosion rate.
inhibitor is added. This fact is attributed to the increment in the charge Fig. 13 shows the equivalent circuits associated with the data

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function of time, Fig. 14. From the Nyquist diagram, one can observe
one single capacitive semicircle whose diameter increases considerably
with the time of immersion. As mentioned above, this increase in the
diameter of the semicircles indicates an increase in the charge transfer
resistance (H. Ashassi-Sorkhabi et al., 2008). It is worth mentioning
that there is apparently a single capacitive semicircle, however, there
are, in fact, two semicircles. The first one appears in the high frequency
region (not visible) and is very small compared to the second one. As a
result, it is not perceptible. In fact, the formation of a small semicircle is
often given in amide and imidazoline fatty acid inhibitor-type systems
(Porcayo-Calderon et al., 2017; Godavarthi et al., 2016; Porcayo-
Calderon et al., 2015a, b).
On the other hand, the bode diagrams allow to track the time
Fig. 13. Equivalent circuits used to adjust the impedance curves. A) in the constant associated with the semicircle in the high frequency region. At
absence of inhibitor, B) adding inhibitor. Rf is the resistance of the inhibitor
the beginning of the test, it is possible to observe a typical response of
film adsorbed, CPEf is the constant phase element of the inhibitor film, and
the solution resistance (high frequency plateau and phase angle °0),
CPEct is the constant phase element of the carbon steel surface.
however, these characteristics are not longer observed at increased
times. Instead, the evolution of a time constant that reaches a maximum
presented in Fig. 12. The equivalent circuits are often used to calculate phase angle of about 64° is observed while the high frequency plateau
electrochemical parameters such as solution resistance, (Rs), charge disappears.
transfer resistance (Rct), and the capacitance of the electrochemical In the intermediate frequency region, a second time constant with a
double layer (Cdl). In the present study, the impedance curve for the phase angle in the range from 50 to 40 Hz is observed. Importantly, this
experiment without inhibitor was fitted to an equivalent Randles circuit time constant only varied at the time of addition of the inhibitor and
(Fig. 13A). Alternatively, two Randles circuits coupled in parallel before reaching the steady state. Thereafter, it returned to the same
(Fig. 13B) were employed to model the experiment with the presence of initial values of time. Finally, in the low frequency region, magnitude
inhibitor. value of the impedance module increased two order of magnitude, and
The constant phase element, CPE, is introduced into the circuit as an the presence of the low frequency plateau is clearly observed, which
ideal double layer capacitor to adjust the data in an accurate way makes infer the presence of a barrier layer on the metallic surface that
(Hassan et al., 2007). The CPE impedance can be expressed as follows: prevents the diffusion of aggressive species towards the metallic sur-
1 face.
ZCPE =
Q (jω)n (7) Table 3 shows the results of the adjustment of the impedance values
obtained with the addition of 25 ppm. At 0 h, the impedance spectra are
Where Q represents a combination of properties related to both the adjusted to the model in Fig. 13A, while, at longer times, these are
electrode surface and the electroactive species, jω is the complex adjusted to the model in Fig. 13B. These values show that the adsorp-
variable for sinusoidal perturbations with ω = 2 πf, and n is the ex- tion of the inhibitor on the surface of the steel has a protective effect.
ponent of the CPE with values between 0 and 1 (Tamilselvi et al., 2006; The formation of a protective film is observed (increase in the values of
Porcayo-Calderon et al., 2014). Previous studies have reported that the Rf and nf, and a decrease in the values of Qf). It is also observed an
exponent “n” can characterize different physical phenomena on the increase in the charge transfer resistance Rct with the immersion time.
surface of the material, such as the lack of homogeneity of the surface, These results indicate a decrease of the active surface caused by the
the presence of impurities, adsorption of the inhibitor, formation of adsorption of the inhibitor on the surface of the steel, decreasing the
layers with porosity, etc. (Bommersbach et al., 2005). corrosion rate (Dong et al., 2011).
The electrochemical parameters obtained from the impedance
curves are shown in Table 2. One can note that Rf values increase when
3.7. Surface morphology
the concentration of the inhibitor is increased. Moreover, the nf values
are greater than that corresponding to the metallic surface. This fact
Fig. 15 presents the optical micrograph of the 1018 carbon steel
indicates a greater capacitance of the system in the presence of inhibitor
surface without inhibitor. The presence of localized corrosion attack
than the unprotected surface. Likewise, with the addition of the in-
(pitting) is observed over the entire surface, possibly due to the pre-
hibitor, a significant increase is observed in the values of Rct. The
sence of chlorides. The degradation of the 1018 carbon steel surface is
maximum charge transfer resistance was obtained after adding 25 ppm
accelerated due to the contact of CO2 dissolved with the water that
of the inhibitor.
produces carbonic acid, as shown in the following reaction:
The present results show that the best inhibitory performance was
obtained with the addition of 25 ppm of inhibitor. Further analysis were CO2 + H2 O ↔ H2 CO3 (8)
carried out to investigate the behavior of adding 25 ppm inhibitor as a
In this type of CO2-saturated solutions, where the corrosive medium
is oxygen free, the degradation of the 1018 carbon steel surface can
Table 2
occurs because of the contact between the anions, HCO3− and CO3−, and
Electrochemical parameters obtained from the impedance curve after 24 h of
the metal surface, as shown in the following electrochemical reactions
immersion.
(Wu et al., 2004; Heydari and Javidi, 2012; Barker et al., 2017):
ppm Rf (Ohm-cm2) Qf (μF cm−2) nf Rct (Ohm-cm2) Qct (μF cm−2) nct
H2 CO3 + 2e− ↔ H+ + 2HCO3− (9)
0 133.9 9.9 × 10−4 0.881
−7
2.5 103.4 3.44 × 10 0.7878 5928 2.22 × 10−5 0.7658 2HCO3− + 2e− ↔ 2CO32 − + H+ (10)
5 223.6 1.11 × 10−6 0.7395 19331 4.46 × 10−6 0.7961
10 2595 1.0 × 10−7 0.8267 28949 1.59 × 10−6 0.7123 (11)
Fe → Fe 2 + + 2e−
25 2676 4.61 × 10−7 0.8075 40597 1.68 × 10−6 0.6555
50 3120 2.8 × 10−7 0.8485 28201 3.722 × 10−6 0.5496
Fe 2 + + 2HCO3− → Fe (HCO3)2 (12)
100 4136 1.9 × 10−7 0.8819 13806 5.66 × 10−6 0.4830

Fe (HCO3)2 → FeCO3 + CO2 + H2 O (13)

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Fig. 14. Evolution of the impedance spectra for the carbon steel 1018 with addition of 25 ppm of inhibitor at 50 °C.

Fe 2 + + CO32 − → FeCO3 (14) sticky and protective films onto metallic surface (Kermani and
Morshed, 2003). Possibly due to the accumulation of these corrosion
Iron carbonates are the most important corrosion products which products on the surface of 1018 carbon steel without inhibitor, more
can be formed at temperatures between 50 and 70 °C and can form a

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Table 3
Evolution of the electrochemical parameters with the addition of 25 ppm of inhibitor.
Time (h) Rf (Ohm-cm2) Qf (μF cm−2) nf Rct (Ohm-cm2) Qct (μF cm−2) nct

0 158.5 5.3 × 10 0.75

3 698.3 1.27 × 10−6 0.6396 8178 6.55 × 10−6 0.6414
6 2144 6.46 × 10−6 0.5950 9622 1.37 × 10−6 0.8039
9 1080 2.44 × 10−7 0.7330 12593 2.25 × 10−6 0.6710
12 1556 1.45 × 10−6 0.7529 16500 2.7 × 10−6 0.7115
18 2597 6.42 × 10−7 0.8042 26858 1.452 × 10−6 0.7159
24 2676 4.61 × 10−7 0.8075 40597 1.68 × 10−6 0.6555

Fig. 15. Surface of the 1018 carbon steel after 24 h without inhibitor at 50 °C.
stable both OCP and RPL values are observed after 8 h of immersion
into corrosive medium. However, RPL values indicate that it does not
improve its corrosion resistance behavior. The observed localized cor-
rosion may be related to the local degradation of the protective layer of
corrosion products, in this case the steel surface covered by the corro-
sion products has a nobler potential (cathode) and the unprotected
areas a more active potential (anode) (Han et al., 2007). Accordingly,
pitting corrosion is initiated at each point where the surface of the alloy
is in direct contact with the corrosive solution, surrounded by the
corrosion products layer on the surface of the alloy.
The surface of the 1018 carbon steel samples corroded with the
addition of different concentrations of inhibitor are shown in Fig. 16. It
is observed the presence of a layer of corrosion products. However, a
smooth surface and uniform corrosion is observed compared to the
samples studied without inhibitor. It is observed that the addition of (5,
10, and 25 ppm) has a lighter degradation, presenting uniform corro-
sion. These results coincide with those obtained by electrochemical
techniques, see Figs. 8 and 9, where the linear polarization resistance
indicates that the addition of the inhibitor adsorbed on the surface of
the material, forming a protective film that prevented the inward dif-
fusion of corrosive species. This fact led to a decrease in the corrosion
rate and avoided localized corrosion, as observed in Fig. 15.
The protective effect of the material is clearly observed with the
addition of the inhibitor and is corroborated by the analysis of the re-
sults, which indicates a beneficial effect of the inhibitor, that is, che-
mically adsorbed on the surface of the 1018 carbon steel. This results
are in agreement with the Langmuir adsorption analysis and RPL re-
sults, suggesting an improvement in the material resistance and

Fig. 16. Surface of the 1018 carbon steel after 24 h with different inhibitor concentrations at 50 °C.

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enhancement of its life time.
4. Conclusions
A modified imidazoline was synthesized from semi-refined rice bran
oil as a renewable agro-industrial source. The modified imidazoline
product was evaluated as a green corrosion inhibitor in a brine-CO2
saturated solution. Imidazoline based on semi-refined rice bran oil
showed good performance as a corrosion inhibitor in 1018 carbon steel
by improving its corrosion resistance in a brine-CO2 saturated solution
at 50 °C. According to the data obtained by polarization curves and OCP
measurements, the effect on the Ecorr corrosion potential drop when
adding the inhibitor, indicating that the rice bran oil-based imidazoline
can be classified as an inhibitor of cathodic type. The results of RPL
measurements indicate that the inhibitor showed a beneficial effect
upon adsorption at the surface of the 1018 carbon steel, forming a
protective film and increasing the corrosion resistance of the material.
The addition of 10 and 25 ppm showed the best resistance to polar-
ization reaching inhibition efficiencies of up to 99.69% and 99.65%,
respectively. The absorption of the imidazoline from rice bran oil fol-
lowed the Langmuir adsorption isotherm and the high value of
O
ΔGads = −53.80 kJ/mol., suggesting that the inhibitor is chemically
adsorbed onto the surface of the 1018 carbon steel. From the EIS
measurements, it is possible to detect the evolution of a time constant in
the high frequency region, which is associated with the process of ad-
sorption of the inhibitor film and the increase in the values of Rct be-
cause of the barrier action of the inhibitor.
Acknowledgments
G. Salinas-Solano is thankful to the postdoctoral fellowship 291053
Consejo Nacional de Ciencia y Tecnología (CONACYT).
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