coatings

Article
Environmentally Benign Grape Seed Oil for Corrosion
Inhibition: Cutting-Edge Computational Modeling Techniques
Revealing the Intermolecular and Intramolecular Synergistic
Inhibition Action
Ahmed Batah 1 , Aisha H. Al-Moubaraki 2 , Ehteram A. Noor 2 , Jamilah M. Al-Ahmari 2 , Azza A. Al-Ghamdi 2 ,
Omar Id El Mouden 1 , Rachid Salghi 1,3 , Maryam Chafiq 4, *, Abdelkarim Chaouiki 4, * and Young Gun Ko 4, *

1 Laboratory of Applied Chemistry and Environment, ENSA, University Ibn Zohr, P.O. Box 1136,
Agadir 80000, Morocco; [email protected] (R.S.)
2 Department of Chemistry, Faculty of Sciences—Alfaisaliah Campus, University of Jeddah,
Jeddah 21589, Saudi Arabia; [email protected] (A.H.A.-M.); [email protected] (J.M.A.-A.)
3 Euromed Research Center, Euromed Polytechnic School, Eco-Campus, Euromed University of Fes,
Fes-Meknes Road, Fes 30030, Morocco
4 Materials Electrochemistry Laboratory, School of Materials Science and Engineering, Yeungnam University,
Gyeongsan 38541, Republic of Korea
* Correspondence: [email protected] (M.C.); [email protected] (A.C.);
[email protected] (Y.G.K.)

Abstract: The growing interest in eco-friendly alternatives has sparked research into essential oils
as corrosion inhibitors, offering an innovative approach. Investigating their unique properties, re-
searchers aim to advance corrosion engineering for a sustainable future. Despite promising lab results,
the exact mechanism of their action in corrosion engineering is not fully understood, highlighting
the need for further exploration. Using computational modeling, we explored how grape seed oil
Citation: Batah, A.; Al-Moubaraki, (GSO) compounds interact with carbon steel (C38) surfaces, unraveling the inhibitive properties
A.H.; Noor, E.A.; Al-Ahmari, J.M.; against corrosion. Employing various simulation methods, such as density functional theory (DFT),
Al-Ghamdi, A.A.; Id El Mouden, O.; density functional-based tight-binding (DFTB), and molecular dynamics (MD), this study validates
Salghi, R.; Chafiq, M.; Chaouiki, A.;
experimental findings and unveils novel insights into the underlying mechanisms of these interac-
Ko, Y.G. Environmentally Benign
tions. Quantitative analysis quantifies the inter- and intramolecular synergistic effect and suggests
Grape Seed Oil for Corrosion
that the LA@OA promotes the charge-transfer process. DFTB calculations reveal that the synergistic
Inhibition: Cutting-Edge
action in the parallel adsorption configuration of LA and OA molecules is sufficiently strong to form
Computational Modeling Techniques
Revealing the Intermolecular and
a stable adsorption layer on the Fe surface with a large negative value of Eads (6.74 eV). Experimental
Intramolecular Synergistic Inhibition results demonstrated that the inhibition performance of GSO extract exhibited a notable increase
Action. Coatings 2024, 14, 77. with increasing concentrations, reaching a higher efficiency of 79% at 0.5 g/L of GSO. EIS results
https://doi.org/10.3390/ demonstrated that the existence of the GSO inhibitor film increases the resistance of the charge
coatings14010077 transfer (about 80 Ω cm2 at 0.5 g/L), indicating the superior barrier anticorrosion properties of the
formed film. The theoretical results validate the exceptional anticorrosion performance and provide
Received: 14 December 2023
Revised: 4 January 2024
compelling evidence of the remarkable ability to prevent corrosion of C38 substrate. The findings
Accepted: 4 January 2024 offer potential pathways for the development of eco-friendly alternatives and interestingly provide a
Published: 5 January 2024 foundation understanding in the field.

Keywords: grape seed oil; synergistic inhibition effect; electrochemistry; electron transfer behavior;
inter-/intramolecular interaction; DFT/DFTB simulations
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and 1. Introduction
conditions of the Creative Commons
Experimental investigations have consistently demonstrated the remarkable adsorp-
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
tion properties of natural oil components towards various environmental materials. How-
4.0/).
ever, due to the intricate and dynamic nature of natural products and their constituents,

Coatings 2024, 14, 77. https://doi.org/10.3390/coatings14010077 https://www.mdpi.com/journal/coatings

Coatings 2024, 14, 77 2 of 20

characterizing the interaction, structure, and dynamics at the molecular scale is a challeng-
ing task that cannot be easily achieved experimentally. Hence, relying solely on laboratory
research has its limitations, and, increasingly, experimentalists are seeking collaborative
solutions through computational techniques. The cutting-edge advancements in computer
science and technology have revolutionized the scientific landscape, enabling researchers
to harness the power of computational methods to enhance their experimental findings
and address some of the most pressing environmental challenges facing our understand-
ing. These computational methods have emerged as a pivotal tool that complements the
traditional laboratory approaches, paving the way for a more efficient and cost-effective
approach to research [1,2]. By combining the power of computer simulations with experi-
mental data, we can unravel the molecular domain and gain a deeper understanding of
the complexities of the natural environment. This synergy between computational and
experimental techniques promises to revolutionize the field of environmental research and
pave the way for innovative solutions for the next generations of science. In this context,
a wide range of computational models and methods are being developed and applied
to investigate the geometric and electronic properties of complexes, including bonding
configuration, adsorption energy, charge-transfer properties, and interaction mechanisms.
The adsorption energy, in particular, is a key parameter that reflects the adsorption capac-
ity of the organic inhibitors and is influenced by various factors, such as the properties
of the compounds and metal surface, the adsorption configuration, and the interaction
mechanism. Furthermore, theoretical analysis can also provide essential molecular-level
insights into the adsorption mechanism beyond just adsorption energy calculations. Based
on the general criterion in the corrosion field, theoretical calculations have been widely
used to support the experimental data or even to correlate some molecular electronic
properties with the inhibition performance of such organic inhibitor. Although there have
been many studies in the corrosion field that have applied computational calculations to
support the experimental data, they have all focused on developing the best formulations
or correlating the molecular electronic properties with the inhibition performance of such
organic inhibitors, and there has been limited research comparing the intramolecular and
intermolecular synergistic inhibition effect of green corrosion inhibitors.
The need for an effective corrosion inhibitor that is both eco-friendly and efficient
is more pressing than ever before. Moreover, the use of acidic solvents is prevalent in
several industrial sectors for various applications, such as cleaning, rust removal, and
descaling [3–5]. Hydrochloric acid, in particular, is one of the most widely used acidic
solvents in various industries [6–8]. In such industries, mild steel is the most commonly
used metal, owing to its excellent mechanical properties, high tensile strength, thermal
stability, manufacturability, and cost-effectiveness [9,10]. However, the susceptibility of
carbon steel (C38) to corrosion in acidic environments, especially in the presence of chloride
ions, is a major concern. The damage caused by corrosion can result in significant safety
issues, production losses, and environmental hazards [11–13]. It is well known that the
corrosion rates are generally governed by several interrelated factors, among them the
phenomenon of diffusion, where the movement of ions can either expedite or retard
corrosion. Temperature, another critical parameter, consistently exerts influence; higher
temperatures generally intensify corrosion reactions. In addition, the conductivity of
the medium significantly impacts corrosion kinetics by influencing the ease with which
electrons move. The type of ions present is a decisive factor, with specific ions either
promoting or inhibiting corrosion. Furthermore, pH levels play a key role in corrosion
dynamics, affecting the electrochemical balance and altering material susceptibility to
degradation. Moreover, the electrochemical potential, a fundamental parameter, governs
the direction and extent of corrosion reactions, influencing the overall rate. Interestingly, the
interconnected nature of these factors collectively shapes the intricate process of corrosion
across diverse environmental conditions [14–17]. To prevent the detrimental effects of
corrosion on carbon steel in acidic environments, the use of corrosion inhibitors has been
widely studied. Corrosion inhibitors work by adsorbing onto the metal surface and forming
Coatings 2024, 14, 77 3 of 20

a protective layer that inhibits the corrosion reaction. A vast number of studies have
been dedicated to the development of efficient corrosion inhibitors for carbon steel in
acidic media. However, many of these inhibitors often suffer from drawbacks, such as
toxicity, high cost, and negative environmental impact [10,18,19]. Therefore, the need
for eco-friendly and efficient corrosion inhibitors for steel in acidic media is of utmost
importance. To address this issue, grape seed oil is one such eco-friendly and efficient
corrosion inhibitor that has shown immense promise in recent studies [20–27]. Grape seed
oil (GSO) is a natural and renewable source of polyphenols, which have been found to
possess excellent antioxidant properties. These properties make grape seed oil a potential
candidate as a corrosion inhibitor for mild steel in acidic environments.
In this context, the potential of grape seed oil as an eco-friendly corrosion inhibitor
for carbon steel in 1.0 M HCl solution is investigated. The inhibiting power of grape oil
was evaluated using gravimetric analyses, electrochemical tests, surface characterization,
as well as DFT simulations. The study reveals that grape oil significantly enhances the
corrosion resistance of C38, acting as a mixed-type inhibitor. The Langmuir isotherm model
was used to evaluate the adsorption of the corrosion inhibition of C38, and the adsorption
thermodynamic parameters were computed and interpreted. Gas chromatography identi-
fied the fatty acids present in grape oil. The results indicate that GSO exhibits significant
corrosion inhibition properties at all concentrations tested and can form a stable adsorption
layer on the surface of C38, even at high temperatures. This work provides valuable in-
sights into the potential of grape seed oil as a promising eco-friendly corrosion inhibitor for
carbon steel in acidic environments. This research presents a comprehensive investigation
into the inhibitory performance of grape seed oil as a corrosion inhibitor for carbon steel
(C38) in hydrochloric acid (HCl) solutions. Moreover, the inter- and intra amolecular
interactions and adsorption patterns of major compounds in grape seed oil molecules on
the metal surface were studied using multiscale computational modeling. The modeling
process involved the use of different simulation techniques, namely density functional
theory (DFT), density functional-based tight-binding (DFTB), and molecular dynamic (MD)
simulations. This was undertaken to both verify the experimental observations and to gain
a better understanding of the types of interactions involved. The findings of this study not
only pave the way for the development of eco-friendly and efficient corrosion inhibitors for
mild steel in acidic environments but also cultivate a complete grasp of new insights into
the mechanisms underlying their interactions.

2. Materials and Methods

2.1. General Computational Details
The use of theoretical chemistry provides a valuable tool for understanding the elec-
tronic properties and adsorption mechanisms underlying the inhibition of corrosion. By
analyzing the properties of the organic–metal interface, including quantum chemical (QC)
properties and interfacial behavior, it is possible to gain insight into the molecular mecha-
nisms underlying corrosion inhibition. To achieve this, various levels of theory, including
DFT, DFTB, and MD modeling, were utilized to study the molecule’s adsorption behavior
and match it with its structural characteristics, providing a comprehensive understanding
of the underlying mechanisms involved. In this vein, and to investigate the interactions
between Fe2+ and grape seed extract components, the molecule complexes were modeled
using Gaussian 16 W software (Rev: C.01) [28], and the interactions were analyzed by
optimizing the geometries of all metal-ion–inhibitor systems in water with the B3LYP
functional and 6-311++G(d,p) basis set [29,30]. The polarizable continuum model (PCM)
model [30] in the Gaussian package was also implemented during the optimization process.
The DFTB method was employed to investigate the interactions between inhibitors and
metal at the molecular level using DFTB+ software (version 1.3). The Slater–Koster trans3d
DFTB parameters, supplemented with an empirical dispersion correction, were utilized
for accurate simulations. To account for Coulombic interactions between atomic partial
charges, a self-consistent charge (SCC) formalism was applied, with an SCC tolerance set
Coatings 2024, 14, 77 4 of 20

to 10−8 , a Broyden mixing scheme, and 0.01 smearing to expedite convergence. For the
bulk lattice optimization, an 8 × 8 × 8 k-points grid in the Brillouin zone was employed,
while a 2 × 2 × 1 k-points grid was used for analyzing molecule–iron interactions. To
represent the iron crystal, it was cleaved along its stable (110) direction, and the resulting
iron layer was utilized for further investigations. MD simulations of the tested molecules
were conducted using the Forcite module within the Materials Studio 2020 package. To
simulate the adsorption behavior of the molecules, the Fe (110) surface was cleaved, and
periodic simulation boxes were established with dimensions of 39.93 × 39.93 × 77.04 Å3 .
Additionally, a vacuum slab of 40 Å was included to replicate real-world conditions. In the
initial MD simulation models, the molecules were randomly positioned in the solution box
at a height of 10 Å from the Fe (110) surface. This deliberate placement aimed to prevent any
immediate impact on the initial electron distribution of the Fe substrate. MD simulations
were carried out under the NVT canonical ensemble at 298 K, employing a COMPASS
force field with a simulation time of 500 ps and a step time of 1 fs. To ensure accuracy,
single energy calculations based on the final equilibrium configurations were performed,
with the bottom iron atoms relaxed. The entire MD calculations were performed with
consistent precision, providing a thorough exploration of the system’s energy and behavior.
Additional details about the computational models used in this study were constructed,
building upon our previous work [31,32].

2.2. Plant Material and GSO Extraction

In August 2022, an extraction process was carried out to obtain grape seed oil (GSO)
from samples collected in the Ouneine commune within the Souss-Massa region of Morocco.
After meticulous cleaning to eliminate impurities, the grape seeds were dried, ground into
small fragments via grinding, and then subjected to hydrodistillation using a Clevenger
apparatus. This distillation process was conducted for 8 h and was repeated three times,
and the average yield was calculated. The resulting GSO was weighed, stored in sealed
dark vials, and kept at a temperature of 5 ◦ C for further analysis. A voucher sample was
placed in the herbarium at the Laboratory of Biotechnology, located within the National
School of Applied Sciences, Ibn Zohr University, Morocco. The chemical composition of
GSO was identified and quantified by gas chromatography coupled with mass spectrometry
(GC/MS). A schematic of GSO extraction and the major available components in the extract
are presented in Figure 1 and Table 1, respectively. The analysis of the results shows that
GSO contains palmitic acid (7.33%), palmitoleic acid (0.098%), heptadecanoic acid (0.067%),
stearic acid (4.52%), oleic acid (19.02%), linoleic acid (67.11%), α-linolenic acid (0.21%),
arachidonic acid (0.20%), gadoleic acid (0.15%), and behenic acid (0.10%).

Table 1. Lipid composition of GSO.

Name Composition (%)

PA 7.33 ± 0.02
PAA 0.098 ± 0.05
HA 0.06 ± 0.01
SA 4.52 ± 0.05
OA 19.02 ± 0.10
LA 67.11 ± 0.12
α-LA 0.21 ± 0.02
AC 0.19 ± 0.02
GA 0.15 ± 0.02
BA 0.10 ± 0.03
The data presented in this study are reported as the mean value with the standard deviation indicated. PA: palmitic
acid; PAA: palmitoleic acid; HA: heptadecanoic acid; SA: stearic acid. OA: oleic acid; LA: linoleic acid; α-LA:
α-linolenic acid; AC: arachidonic acid; GA: gadoleic acid; BA: behenic acid.
 Coatings 2024, 14, x FOR PEER REVIEW 5 of 22
Coatings 2024, 14, 77 5 of 20

Figure 1.
Figure 1. Schematic
Schematicof GSO extraction
of GSO and the
extraction andmajor available
the major components
available in the extract.
components in the (a) Sche-
extract.
matic illustration of the extraction process. (b) Structure of a ripe grape berry. (c) Electrostatic
(a) Schematic illustration of the extraction process. (b) Structure of a ripe grape berry. (c) Elec- po-
tential distribution on the whole molecular surface of major components in the extract.
trostatic potential distribution on the whole molecular surface of major components in the extract.

Table
2.3. 1. Lipid
Weight composition
Loss of GSO. Techniques
and Electrochemical
The investigation Namefocused on assessing the corrosion rate and inhibition
Composition (%) performance
of GSO extract for C38PA steel in an HCl environment, employing 7.33 the weight
± 0.02 loss method at a
temperature of 298 K. The procedure involved meticulously drying and weighing the metal
PAA 0.098 ± 0.05
sample surfaces of each steel specimen after they were washed and immersed in corrosive
HA 0.06 ± 0.01
solutions with and without the inhibitor for 24 h. The specimens were collected, cleaned,
dried, and then reweighted by high-precision analytical balance4.52
SA ± 0.05
to determine the corrosion
OA 19.02 ± 0,10
rate. The electrochemical characteristics were assessed in 1 M HCl solution utilizing
both potentiodynamic LApolarization (PDP) and electrochemical 67.11 ± 0,12
impedance tests. These
α-LA
evaluations were performed utilizing a three-electrode system, 0.21 ± 0.02
consisting of a working
electrode with a 1 cm2AC exposed area, a platinum plate functioning 0.19as±the
0.02counter electrode,
and Ag/AgCl serving GA as the reference electrode. The testing 0.15 ± 0.02 employed was
equipment
the Corrtest Volta lab BA potentiostat/galvanostat, which was manufactured0.10 ± 0.03 in Hubei, China.
All electrochemical measurements were performed in 1 M HCl solution with and without
The data presented in this study are reported as the mean value with the standard deviation indi-
different
cated. PA:concentrations of GSO
palmitic acid; PAA: extract.
palmitoleic Prior
acid; toheptadecanoic
HA: polarization acid;
measurement, the working
SA: stearic acid. OA: oleic
electrode was immersed
acid; LA: linoleic acid; α-LA:inα-linolenic
the HCl solution
acid; AC:for 30 min toacid;
arachidonic obtain
GA:agadoleic
relatively stable
acid; open-
BA: behenic
circuit
acid. potential (OCP). The potentiodynamic scans were carried out over a potential
range of −0.8 to +0.2 V relative to the OCP at a scan rate of 1 mV s−1 . Meanwhile, the
electrochemical
2.3. Weight Loss impedance spectroscopy
and Electrochemical (EIS) measurements were performed by applying
Techniques
AC voltage
The investigation focused on assessing0.01
with frequency ranging from the to 105 Hz rate
corrosion at anandamplitude
inhibition ofperformance
10 mV rms
sinusoidal perturbation vs. OCP. All electrochemical experiments were
of GSO extract for C38 steel in an HCl environment, employing the weight loss method repeated at least
at
three times to ensure
a temperature of 298reproducibility.
K. The procedure involved meticulously drying and weighing the
The examination of thermodynamic activation parameters in response to tempera-
metal sample surfaces of each steel specimen after they were washed and immersed in
ture variations was conducted through experiments employing the PDP method. These
corrosive solutions with and without the inhibitor for 24 h. The specimens were collected,
experiments were systematically performed at different temperatures, ranging from 298 K
cleaned, dried, and then reweighted by high-precision analytical balance to determine the
to 328 K. Detailed information regarding the experimental apparatus can be found in our
corrosion rate. The electrochemical characteristics were assessed in 1 M HCl solution uti-
previous research [33–36].
lizing both potentiodynamic polarization (PDP) and electrochemical impedance tests.
These evaluations were performed utilizing a three-electrode system, consisting of a
Coatings 2024, 14, 77 6 of 20

3. Results and Discussion

3.1. Revealing Nature’s Strength: Understanding the Corrosion Inhibition Mechanisms of GSO
through Computational Perspectives
To elucidate the mechanism by which GSO components act as corrosion inhibitors,
the inhibitory properties of major components on corrosion were analyzed through quan-
tum chemical calculations, providing insights into their adsorption mechanism on metal
surfaces. The study found that two key molecules—oleic acid (OA) and linoleic acid
(LA)—played a synergistic role in inhibiting corrosion, as shown in Figure 2. Analysis
of the molecules’ frontier molecular orbital (FMO) distribution revealed that the highest
occupied molecular orbital (HOMO) was mainly located on the aliphatic chain (Figure 2b),
particularly the central carbon–carbon bond (C=C) while the lowest unoccupied molecular
orbital (LUMO) was primarily distributed on the carboxyl group (–COOH) (Figure 2c). Ac-
cording to FMO theory, we can infer that the inhibitor molecule’s HOMO donates electrons
to an Fe 3d empty orbit to form coordination bonds and the electron-accepting ability of
–COOH groups is reflected in the location of their LUMO orbitals. These findings offer
insights into the adsorption active sites of the inhibitor molecules and shed light on the
mechanism underlying their corrosion inhibition properties. To gain a better understanding
of how OA@LA molecules adhere to the C38 surface, total density of state (TDOS) and
partial density of state (PDOS) of the OA@LA system were provided. Based on the TDOS
and PDOS, the chemical reaction occurs due to interactions between LA and OA inhibitors,
and the hybridization peak is mainly located within the region of 0 to 5 eV and −12 to
−8 eV. Moreover, it is found that in most valence molecular orbitals, the LA and OA have
comparable amounts of contribution, indicating that the synergistic between LA and OA
molecules enhances the electron transfer characteristics of the system. The positive and
negative regions in the OPDOS indicate the presence of bonding and antibonding molecular
Coatings 2024, 14, x FOR PEER REVIEW 7 of 22
orbitals, respectively, within the energy range corresponding to the strong hybridization
between the two inhibitor molecules.

Figure 2. Electronic and physicochemical properties of LA@OA system based on FMO density dis-
Figure 2. Electronic and physicochemical properties of LA@OA system based on FMO density
tributions. (a) Optimized structure; (b) HOMO; (c) LUMO; (d) TDOS, PDOS, and OPDOS of the
distributions.
LA@OA system. (a) Optimized structure; (b) HOMO; (c) LUMO; (d) TDOS, PDOS, and OPDOS of the
LA@OA system.
To quantitatively discuss the inter- and intramolecular synergistic effect of OA@LA,
electrostatic potential (ESP) distribution, ESP-mapped molecular vdW surface, reduced
density gradient (RDG), interaction region indicator (IRI), and average local ionization
energy analysis (ALIE) were conducted. Figure 3a,b clearly reveal the charge distribution
and possible reaction sites. The green color indicates the positively charged regions, while
the red color suggests negatively charged regions. As displayed in Figure 3a, the ESP of
Coatings 2024, 14, 77 7 of 20

To quantitatively discuss the inter- and intramolecular synergistic effect of OA@LA,

electrostatic potential (ESP) distribution, ESP-mapped molecular vdW surface, reduced
density gradient (RDG), interaction region indicator (IRI), and average local ionization
energy analysis (ALIE) were conducted. Figure 3a,b clearly reveal the charge distribution
and possible reaction sites. The green color indicates the positively charged regions, while
the red color suggests negatively charged regions. As displayed in Figure 3a, the ESP of the
molecular surface near the oxygen atoms has the most negative value (−43.28 kcal/mol,
−30.85 kcal/mol), owing to the negative contribution of lone-pair electrons of –COOH
groups. In addition, the carbon–carbon bonds occupy the green area with smaller ESP
values, indicating that these regions are also considerable for chemical reaction. Cyan and
yellow spheres correspond to the minima and maxima of ESP points, respectively. As
displayed in Figure 3c,d, the value and the corresponding color reveal that the hydrogen
bond (blue isosurface) and vdW interaction (green isosurface) play a decisive role in the
noncovalent interaction between LA and OA molecules. Interestingly, the IRI isosurface
in Figure 3e indicates that electron density in the central carbon–carbon bond region of
the LA molecule is large and implies that the bonding effect is strong, suggesting the
intermolecular charge transfer between the bonding and antibonding orbitals. The latter
plays a dominant role in synergistic action between LA and OA molecules. These results
are confirmed by the ALIE isosurface (Figure 3f), in which cyan spheres correspond to the
minimum points of the ALIE on the surface of LA@OA system, which reflected the sites
where the electrophilic reaction was easy to occur. The blue color highlights the regions
with relatively low ALIE values, which means that these regions are more prone to the
Coatings 2024, 14, x FOR PEER REVIEW 8 of 2
electrophilic reaction. Results from the ALIE demonstrate that the C=C group also made a
greater contribution for providing lone-pair electrons.

Figure 3.potential
Figure 3. (a) Electrostatic (a) Electrostatic potential
(ESP); (b) (ESP); (b)distribution
ESP statistical ESP statistical
on distribution on LA@OA
LA@OA molecular molecular sur
surface
face area with isosurface = 0.002 (surface local maxima and minima of ESP are marked with yellow
area with isosurface = 0.002 (surface local maxima and minima of ESP are marked with yellow
and cyan spheres, respectively). The weak interaction regions characterized by (c) RDG isosurface
and cyan spheres,(d) respectively). The
scatter plot of RDGweak interaction
versus electron regions
density characterized
(ρ) multiplied by
by (c)
the RDG isosurface;
sign of the second Hessia
(d) scatter plot ofeigenvalue
RDG versus electron density (ρ) multiplied by the sign of the second
(λ2); (e) interaction region indicator (isosurface = 2); (f) ALIE isosurfaceHessian
and the mini
mum
eigenvalue (λ2 ); (e) points distribution
interaction on LA@OA
region indicator molecular
(isosurface = 2);area (unit:isosurface
(f) ALIE kcal/mol). and the minimum
points distribution on LA@OA molecular area (unit: kcal/mol).
To study the inter- and intramolecular synergistic action of LA@OA on the charge
transfer behavior between LA@OA and an Fe atom, the electronic properties of th
LA@OA–Fe system were explored by DFT calculations. The optimized complex mode
based on a single optimized LA@OA and one Fe atom reveals that LA and OA molecule
are positioned in a parallel arrangement and effectively coordinate with the Fe atom (Fig
ure 4a). The synergistic action of LA@OA with metal can be explained on the basis of th
distribution of MO energy levels and inter-–intrafragment interactions. The low-lying
 Coatings 2024, 14, 77 8 of 20

To study the inter- and intramolecular synergistic action of LA@OA on the charge-
transfer behavior between LA@OA and an Fe atom, the electronic properties of the
LA@OA–Fe system were explored by DFT calculations. The optimized complex model
based on a single optimized LA@OA and one Fe atom reveals that LA and OA molecules
are positioned in a parallel arrangement and effectively coordinate with the Fe atom (Fig-
ure 4a). The synergistic action of LA@OA with metal can be explained on the basis of the
distribution of MO energy levels and inter—intrafragment interactions. The low-lying
HOMO orbitals are formed by combining the orbitals of the metal and the LA@OA in a
specific way, which results in a derivative of their combination (Figure 4b). It is clear from
Figure 4c that the energy gap is significantly decreased from 5.83 eV to 2.88 eV, which
Coatings 2024, 14, x FOR PEER REVIEW
indicates that the LA@OA promotes charge transfer to form stable complexes with the Fe9 of 22
surface. Notably, the synergistic effects of δg inter (mainly with COOH groups) and δg intra
(tail of the molecule) made these interactions strong to form stable complexes and strong
interactions with the Fe atom (Figure 4d–f).

Figure
Figure 4. 4. (a–c)
(a–c) Theelectronic
The electronic properties
properties and
andcharge-transfer behavior
charge-transfer of LA@OA
behavior of LA@OAinteracted with Fe
interacted with Fe
and its molecular orbital interactions. (d,e) IGM analysis and (f) scatter plots of RDG showing
and its molecular orbital interactions. (d,e) IGM analysis and (f) scatter plots of RDG showing the the
inter-
inter- andand intramolecular interaction.
intramolecular interaction.

To further clarify the synergism action and the donor–acceptor relationship in the
To further clarify the synergism action and the donor–acceptor relationship in the
LA@OA system, Hirshfeld surface (HS) and fingerprint plot analyses were performed by
LA@OA system,
evaluating Hirshfeld
the electron surface
density with(HS) and fingerprint
promolecular plot analyses
approximation, were
as shown inperformed
Figure 5. by
evaluating the electron
The isosurface in Figuredensity with promolecular
5a,b displayed the HS of the approximation,
LA and OA fragments,as shown in Figure 5.
and dnorm
The is isosurface
the mappedinfunction.
Figure 5a,b
Thedisplayed the HSa of
red parts exhibit the dnorm
small LA andvalue
OA fragments,
and indicateand dnorm
close
is the mapped function. The red parts exhibit a small dnorm value and indicate close prox-
proximity, which is a result of H-bond interaction. Additionally, in the fingerprint plot
(Figure
imity, 5c,d),
which is only oneof
a result spike at theinteraction.
H-bond bottom left region for both in
Additionally, systems (i.e., LA onto
the fingerprint plotOA
(Figure
and OA onto LA) was detected. The results indicate that the LA molecule
5c,d), only one spike at the bottom left region for both systems (i.e., LA onto OA and OAworks as the
hydrogen bond acceptor because the value of di is larger than de , while the OA molecule
onto LA) was detected. The results indicate that the LA molecule works as the hydrogen
behaves as the H-bond donor due to the smaller di value. These findings confirm again
bond acceptor because the value of di is larger than de, while the OA molecule behaves as
the strong donor–acceptor behavior as well as the inter-/intramolecular synergistic effect
thebetween
H-bondLAdonor
and OA due to the smaller di value. These findings confirm again the strong
molecules.
donor–acceptor behavior as well as the inter-/intramolecular synergistic effect between
LA and OA molecules.
Coatings 2024, 14, x FOR PEER REVIEW 10 of 22
Coatings 2024, 14, 77 9 of 20

Figure
Figure5.5.The Hirshfeld
The surface
Hirshfeld analysis
surface andand
analysis corresponding fingerprint
corresponding plot: plot:
fingerprint (a,c) LA onto
(a,c) LAOA;
onto(b,d)
OA;
OA onto LA.
(b,d) OA onto LA.

In
Inorder
order to to determine
determine the the interfacial
interfacial mechanism
mechanism and and adsorption
adsorptionconfiguration
configurationof of
LA@OA,
LA@OA,first-principles
first-principlesDFT DFTcalculations
calculationswere wereconducted.
conducted.Two Twoinitial
initialconfigurations
configurationsof of
LA@OA
LA@OAwere wereconsidered,
considered,and andtheir
theircorresponding
correspondingstable stableconfigurations
configurationsare aredisplayed
displayedinin
Figure
Figure6.6.The
Theresults
resultsshowshowthatthatLALAand andOA OAmolecules
moleculesinintheir theirparallel
paralleland andperpendicular
perpendicular
patterns
patternshave
haveaatendency
tendencytotomigrate
migratetoward
towardthe theFe Feinterface
interfaceand andinteract
interactwith withititvia
viaCOOH
COOH
groups.Compared
groups. Compared with initial configurations
configurations(inset), (inset),thetheside
sideandand toptopviews
viewsof of
both geome-
both ge-
tries clearly
ometries indicate
clearly indicatethatthat
thethe
adsorption
adsorption of LA
of LA andandOA OA molecules
molecules is is
through
through the
thebonding
bond-
of O
ing ofatoms
O atoms on the Fe surface.
on the Fe surface.As expected,
As expected, the parallel
the parallelconfiguration
configuration is energetically more
is energetically
favorable,
more suggesting
favorable, suggestingthe formation
the formation of a of
more stable
a more structure
stable structurewhichwhich cancanmaximize
maximize the
surface
the coverage
surface coverage of Fe (Figure
of Fe (Figure6a).6a).
Further,
Further, thethe
significant
significant alteration
alteration in in
thethegeometry
geometry re-
sulting from vertical adsorption is likely due to the inclination
resulting from vertical adsorption is likely due to the inclination of the molecules to as- of the molecules to assume
an angled
sume position
an angled as compared
position as compared to the to initial
the initialconfiguration
configuration (Figure
(Figure6b).6b).The adsorption
The adsorp-
energy (E
tion energy (Eads) for each optimized model was calculated, and the results reveal the
ads ) for each optimized model was calculated, and the results reveal that thatinter-
the
and intramolecular
inter- and intramolecular synergistic action
synergistic in the
action inparallel adsorption
the parallel adsorption configuration
configuration of LA and
of LA
OA OA
and molecules
molecules is sufficiently strong
is sufficiently to form
strong uniform
to form and stable
uniform adsorption
and stable adsorptionlayerslayers
on theonFe
surface with a large negative value of E ( − 6.74 eV). Owing to
the Fe surface with a large negative value of Eads (−6.74 eV). Owing to the synergistic action
ads the synergistic action of
LA@OA, the adsorption of LA and OA molecules in their
of LA@OA, the adsorption of LA and OA molecules in their vertical geometry retains vertical geometry retains strong
interaction
strong with Eads
interaction with =− 6.10
Eads eV, which
= −6.10 demonstrates
eV, which the adsorption
demonstrates capability
the adsorption of LA and
capability of
OA molecules. This is also confirmed by the bond lengths
LA and OA molecules. This is also confirmed by the bond lengths of O–Fe in both parallel of O–Fe in both parallel and
perpendicular
and perpendicular configurations
configurations which
which are are
withinwithinthe the
rangerangeof 2.01–2.31
of 2.01–2.31 Å. These
Å. These values are
values
close
are to the
close sum
to the sumof the
of thecovalent radii
covalent of O
radii ofand
O and Fe (r
Fecov (O–Fe)
(rcov = 0.69 Å + 1.32 Å = 2.01 Å).
(O–Fe) = 0.69 Å + 1.32 Å = 2.01 Å).
Coatings 2024, 14, 77 Coatings 2024, 14, x FOR PEER REVIEW 10 of 20 11 of

Figure 6. The side and top views of the final configuration for a combination of LA and OA mo
Figure 6. The side and top views of the final configuration for a combination of LA and OA molecules
cules adsorbing on Fe(110) surface. (a) Parallel and (b) perpendicular adsorption patterns. The in
adsorbing on Fe(110) surface. (a) Parallel and (b) perpendicular adsorption patterns. The inset
structure is the initial structure before adsorption.
structure is the initial structure before adsorption.
We can infer that the adsorption ability of LA and OA molecules on the Fe surface
We can infer that the
mainly dueadsorption abilityeffect
to the synergistic of LA ofand OA molecules
LA@OA, on the
which greatly Fe surface
enhances is
the electron tra
mainly due to the synergistic effect of LA@OA, which greatly enhances the electron transfer
fer and bonding interaction and thereby the formation of stable inhibitor films with
and bonding interaction
ceptionaland thereby
corrosion the formation
protection. of stable inhibitor
The synergistic films
action and with exceptional
adsorption behavior of LA a
corrosion protection.
OA wereThealso
synergistic
simulated action
by MD and adsorption
simulations. behavior
Figure of LAthe
7 displays andadsorption
OA were behavior
also simulated by LAMDand simulations.
OA moleculesFigureduring7adisplays
simulationthetime
adsorption
of 500 ps.behavior of LA and
Comparatively, the behavior
OA molecules during a simulation time of 500 ps. Comparatively, the behavior of
LA and OA is changed after 100 ps of MD, and the inhibitor molecules could adsorbLA and
OA is changed the after
Fe100 ps ofvia
surface MD, and theacid
carboxylic inhibitor
as themolecules
main activecould
groupsadsorb on the
to form Fe
coordinate bon
surface via carboxylic acid as the main active groups to form coordinate bonds (Figure 7b).
After 250 ps, it is observed that LA and OA molecules are oriented parallel to the Fe (110)
Coatings 2024, 14, x FOR PEER REVIEW 12 of 22

Coatings 2024, 14, 77 11 of 20

(Figure 7b). After 250 ps, it is observed that LA and OA molecules are oriented parallel to
the Fe (110) plane surface, representing the high ability of these molecules to adsorb on
the Fesurface,
plane surface representing
via parallel configuration
the high ability (Figure 7c).molecules
of these The finalto configuration
adsorb on the after 500 ps
Fe surface
(Figure 7d) configuration
via parallel shows that LA and OA
(Figure 7c). are
Themore attracted to the
final configuration metal
after 500 surface and
ps (Figure 7d)that the
shows
biggest
that LAchange
and OA in are
the more
adsorption behavior
attracted to theofmetal
LA and OA molecules
surface caused
and that the by their
biggest changeinter-
in
action with the behavior
the adsorption Fe surfaceofisLA
affected
and OA bymolecules
the synergistic action
caused of LA@OA,
by their which
interaction withhelps to
the Fe
surface isthe
enhance affected
surfacebycoverage
the synergistic action of strong
and, therefore, LA@OA, which
inter- andhelps to enhanceinteractions
intramolecular the surface
coverage
[37–41]. and, therefore, strong inter- and intramolecular interactions [37–41].

Figure 7. Adsorption behavior of LA and OA molecules simulated by MD simulations. Geometrical

and
and configurational changes after
configurational changes after (a)
(a) 20
20 ps,
ps, (b)
(b) 100
100 ps,
ps, (c)
(c) 250
250 ps,
ps, and
and (d)
(d) 500
500 ps.
ps.

3.2. Anticorrosion
3.2. Anticorrosion Performance
Performance
Experimental investigations
Experimental investigations were
were carried
carried out
out to
to examine
examine the the impact
impact ofof inhibitor
inhibitor con-
con-
centration on the efficacy of corrosion rate inhibition at 298 K in the absence and
centration on the efficacy of corrosion rate inhibition at 298 K in the absence and presence presence of
the GSO inhibitor. The results revealed that with increasing inhibitor concentration,
of the GSO inhibitor. The results revealed that with increasing inhibitor concentration, the the in-
hibition efficiency
inhibition improved,
efficiency improved,indicating that at
indicating higher
that concentrations,
at higher the inhibitor
concentrations, formed
the inhibitor
a more compact layer on the C38 surface due to better adhesion of inhibitor
formed a more compact layer on the C38 surface due to better adhesion of inhibitor mol- molecules to
the metallic surface. Additionally, the results depicted in Figure 8a demonstrate
ecules to the metallic surface. Additionally, the results depicted in Figure 8a demonstrate that an
increase
that in inhibitor
an increase concentration
in inhibitor resultedresulted
concentration in a decrease in the corrosion
in a decrease rate values
in the corrosion rate due
val-
to an increase in the covering surface area on the metal surface [42–44].
ues due to an increase in the covering surface area on the metal surface [42–44]. These These outcomes
are attributed
outcomes to the accumulation
are attributed and adsorption
to the accumulation activities ofactivities
and adsorption the GSOof molecules
the GSO on the
mole-
metallic surface [45–49]. Therefore, it can be hypothesized that an increase in
cules on the metallic surface [45–49]. Therefore, it can be hypothesized that an increase in inhibitor con-
centration leads to a significant improvement in adsorption up to the optimal concentration
inhibitor concentration leads to a significant improvement in adsorption up to the optimal
of 0.5 g/L, which results in complete coverage of all active zones on the surface exposed to
the corrosive medium. To comprehend the protective mechanism of the GSO inhibitor, a
Coatings 2024, 14, 77 12 of 20

polarization test was carried out (depicted in Figure 8b). The outcomes showed that the
protective mechanism remained consistent across different inhibitor concentrations. From
PDP results, compared with the blank sample, the cathode slope of the solution with the
GSO extract has no obvious change, and the anode slope has obvious change, indicating
that the GSO extract can alter the anodic dissolution of C38 steel. At the same time, the
similarity in shape in both uninhibited and inhibited solutions indicates that the C38 steel
corrosion reaction mechanism does not change after the addition of GSO extract, which
is well-observed from the parallel form of cathodic lines. It is crucial to recognize that
multiple factors can influence electrode polarization. When corrosion inhibitors are intro-
duced into the solution, their molecules tend to adsorb onto the surface of the carbon steel,
forming a protective film. This adsorption alters the properties of the interface between
the solution and the carbon steel, thereby influencing the observed changes in the Tafel
parameters [50,51]. On the other hand, in line with findings from several investigations, the
deviation observed in the corrosion potential (Ecorr ) towards anodic or cathodic potentials
serves as a crucial parameter for characterizing the type of tested inhibitor. Generally, a shift
surpassing 85 mV classifies the compound as either an anodic or cathodic inhibitor, while
a shift below 85 mV suggests a predominantly mixed-type inhibition mechanism. Upon
meticulous examination of the Ecorr values presented in Table 2, it is apparent that across
all tested concentrations relative to the blank test, the displacement remains consistently
below 85 mV. This consistent trend indicates that GSO extract primarily functions as a
mixed-type inhibitor. Mixed-type inhibitors reduce the corrosion rate of both anodic and
cathodic reactions without inducing changes to the corrosion mechanism. Additionally,
the computed electrochemical parameters (outlined in Table 2) revealed that an increase in
GSO extract concentration resulted in the development of a superior protective film and a
reduction in the corrosion rate. At the same time, the inhibition efficiency of the extract
inhibitor increases with the increase in GSO concentration. The effect of different concentra-
tions of GSO on the characteristics of the anticorrosion barrier formed on the C38 substrate
was evaluated using the EIS method (Figure 8c–e). To decouple the various electrochemical
processes occurring at the metal–solution interface, each impedance response was fitted,
and the fitting process considered both the physical and chemical conditions of the system.
The impedance responses were interpreted using a circuit model, as illustrated in Figure 8c
(inset). In this model, the fitting parameters Rs and Rct represent the solution resistance
and charge-transfer resistance, respectively. Additionally, the model incorporates the CPE,
which signifies the double-layer capacitance and is defined by its components, namely
admittance (Q) and exponent (n). Introducing the CPE in lieu of a purely capacitive ele-
ment played a vital role in addressing the heterogeneity inherent in the working electrode.
Considering the real-world corrosion process in practical environments, the significance
of capacitance was deemed minimal, particularly because corrosion typically does not
involve an external source of electrical current. Consequently, when characterizing the
corrosion properties of the protective layer, the effectiveness of the extract in inhibiting
corrosion could be assessed through the evaluation of the charge-transfer resistance param-
eter. The Nyquist and Bode diagrams revealed that the inhibitory effect was significantly
enhanced as the concentration of the inhibitor increased, reaching an optimal concentration
of 0.5 g/L. These findings were further corroborated by the fitting of the EIS data presented
in Table 3. The impedance responses for all systems and concentrations consisted primarily
of one capacitive loop and one inductive loop at high and low frequencies, respectively.
The results suggested that all the systems with the inhibitor exhibited similar behavior,
indicating a comparable corrosion inhibition effect. However, at the optimal concentration,
larger capacitive loops were observed, indicating superior performance against corrosion
of the C38 substrate (Table 3). Therefore, it can be concluded that the C38 surface was
more thoroughly covered by adsorbed layers of GSO at an optimal concentration of 0.5 g/L
when displacement reactions occurred between the metal and inhibitor. This efficient
blocking of charge and mass transfer resulted in the reduction in the corrosion of the metal
alloy [52]. In addition, the effectiveness of corrosion inhibitor on a metal substrate was
Coatings 2024, 14, x FOR PEER REVIEW 14 of 22

Coatings 2024, 14, 77 occurred between the metal and inhibitor. This efficient blocking of charge and mass 13 of 20
transfer resulted in the reduction in the corrosion of the metal alloy [52]. In addition, the
effectiveness of corrosion inhibitor on a metal substrate was examined through adsorption
isotherms,
examined which
through can reveal how
adsorption inhibitorwhich
isotherms, particles directly
can reveal howor inhibitor
indirectlyparticles
adsorb directly
to the
metal surface and reduce contact between aggressive species and the metal.
or indirectly adsorb to the metal surface and reduce contact between aggressive species Various mod-
and
els, including the Langmuir, Temkin, and Freundlich, were assessed to determine
the metal. Various models, including the Langmuir, Temkin, and Freundlich, were assessed the most
appropriate
to determine adsorption isotherm. Results
the most appropriate showed
adsorption that the
isotherm. Langmuir
Results showedmodel
thatwas
the the most
Langmuir
suitable,
model wasas evidenced by a slope
the most suitable, as and regression
evidenced by acoefficient
slope and nearing
regressionunity (Figure nearing
coefficient 8f). By
analyzing the K8f).
unity (Figure ads values (Table 4),
By analyzing theitKwas
ads
concluded
values (Tablethat
4), the
it GSO
was components
concluded that had
the the
GSO
strongest affinity for adsorbing onto the C38 surface. A higher K value indicated
components had the strongest affinity for adsorbing onto the C38 surface. A higher Kads
ads a more
robust
value and effective
indicated adsorbed
a more robustlayer
and on the metal
effective surface,
adsorbed resulting
layer on theinmetal
superior surface
surface, cov-
resulting
erage [50,53–55].
in superior surface coverage [50,53–55].

Figure 8. Anticorrosion performance results of GSO. (a) Variation of CR and inhibition performance
Figure
with the 8. Anticorrosion
concentration of performance
GSO inhibitorresults
in 1.0 of
MGSO. (a) Variation
HCl. (b) of Ccurves
Polarization R and of
inhibition
C38 with performance
and with-
out GSO at 298 K. (c–e) Nyquist (inset: equivalent electrical circuit employed for fittingand
with the concentration of GSO inhibitor in 1.0 M HCl. (b) Polarization curves of C38 with EISwithout
data),
Bode
GSOimpedance modulus,
at 298 K. (c–e) and
Nyquist phase
(inset: angle plots
equivalent for C38circuit
electrical corrosion, respectively.
employed (f) EIS
for fitting Langmuir ad-
data), Bode
sorption
impedanceisotherm of GSO
modulus, andon the C38
phase anglesurface at 298
plots for C38K. corrosion, respectively. (f) Langmuir adsorption
isotherm of GSO on the C38 surface at 298 K.
Table 2. Polarization parameters of C38 in the presence of varying concentrations of GSO at 298 K.
Table 2. Polarization parameters of
Concentration −EC38
corr
in the presence
−βc of varyingβaconcentrations of GSO at IE
Icorr 298I K.
Inhibitor
(g/L) (mV/SCE) (mV dec −βc )
−1 (mV decβa )
−1 (μA cm−2) (%)
1M HCl
Inhibitor
Concentration
- 463.1−±E0.5
corr 168.2(mV
± 0.5 123.4(mV
± 0.6 Icorr
636.1 ± 0.4 IEI
-
(g/L) (mV/SCE) (µA cm−2 ) (%)
0.5 465.2 ± 0.2 191.7 ± −0.2
dec 1)
76.3 ± −0.7
dec 1)
147.1 ± 0.3 76.98
1 M HCl 0.3 - 464.1 ± 0.1
463.1 ± 0.5 196.8
168.2± ±
0.60.5 73.8
123.4± ±
0.20.6 238.2 ± 0.7
636.1 ± 0.4 62.67
-
GSO ± 0.2 195.4
191.7± ± 76.3±±0.4 147.1 ±
0.10.5 465.2
470.0 ± 0.3 0.10.2 94.4 0.7 287.0 0.3
± 0.5 76.98
54.97
464.1 ± 0.1 196.8 ± 0.6 73.8 ± 0.2 238.2 ± 0.7
GSO 0.050.3 470.5 ± 0.2 194.6 ± 0.8 80.1 ± 0.3 328.1 ± 0.2 62.67
48.42
0.1 470.0 ± 0.3 195.4 ± 0.1 94.4 ± 0.4 287.0 ± 0.5 54.97
0.05 470.5 ± 0.2 194.6 ± 0.8 80.1 ± 0.3 328.1 ± 0.2 48.42
Coatings 2024, 14, 77 14 of 20

Table 3. The EIS parameters estimated from the impedance spectra of C38 with and without GSO at
298 K.

Concentration
Inhibitor Rct (Ω cm2 ) Cdl (µF/cm2 ) Ect (%)
(g/L)
1 M HCl - 18.1 ± 1.5 221.16 ± 2.05 -
0.5 80.2 ± 0.6 132.69 ± 1.15 77.5
0.3 50.1 ± 0.8 212.31 ± 1.98 64.0
GSO
0.1 40.2 ± 0.7 265.39 ± 0.87 55.1
0.05 35.1 ± 0.9 303.30 ± 1.26 48.57

Table 4. Linear regression parameters obtained from fitted line of Figure 8f.
◦
Inhibitor Kads (L/g) R2 ∆Gads (kJ/mol)
GSO 2.16 0.99042 −11.85

The inhibitory effect of natural GSO on steel corrosion at different inhibitor concentra-
tions was investigated over a temperature range of 298 to 328 K. Polarization curves of C38
were obtained in a 1 M HCl medium before and after adding GSO at a concentration of
0.5 g/L, following a 30 min immersion time. Figure 9a,b show the effect of temperature
on the polarization curves of steel without and with the optimal concentration of GSO,
respectively. Table 5 presents the corrosion current densities (Icorr ), steel corrosion poten-
tials (Ecorr ), Tafel slopes, and inhibitor efficiency as a function of temperature. The results
indicate that temperature has no significant effect on the overall shape of the polarization
curve’s cathodic and anodic branches and only slightly alters the steel’s corrosion poten-
tial (Ecorr ) in 1 M HCl, both with and without the inhibitor. However, current densities
increase as temperature increases. The cathodic curves are parallel, indicating the pure
activation mechanism of H+ ion reduction on the steel surface throughout the temperature
range [56–58]. Furthermore, the increase in corrosion current with the temperature in the
presence of the inhibitor is much lower than in the control, confirming the strength of GSO
as an inhibitor over the studied temperature range. From Figure 9c,d, the calculated value
of Ea is higher than the value obtained without inhibitor (Table 6), suggesting that GSO
has a potent inhibitory effect by raising the energy barrier for the corrosion process. The
positive signs of the enthalpies (∆H*) reflect the endothermic nature of the steel dissolu-
tion process [59,60]. Additionally, it is observed that the activation energy and activation
enthalpy vary depending on the inhibitor concentration, indicating that the dissolution
reaction will be further blocked on the metallic surface sites [61–63]. Moreover, the high
negative values of ∆S* during the activation process can be attributed to the formation
of an activated complex represented by association or fixation, resulting in losses in the
degrees of freedom of the system during the inhibition process [64–66].

Table 5. Temperature effect on electrochemical parameters.

Temperature −Ecorr Icorr − βc EI

Medium
(K) (mV/SCE) (µA/cm2 ) (mV/dec) (%)
298 ± 1 463.1 ± 0.5 636.1 ± 0.4 168.2 ± 0.5 -
308 ± 1 467.2 ± 0.2 896.4 ± 0.2 165.1 ± 0.1 -
1 M HCl
318 ± 1 470.1 ± 0.6 3428.1 ± 0.7 167.4 ± 0.6 -
328 ± 1 477.0 ± 0.8 6720.2 ± 0.7 164.3 ± 0.8 -
298 ± 1 465.2 ± 0.2 147.1 ± 0.3 191.7 ± 0.2 76.98
1 M HCl + 308 ± 1 477.4 ± 0.3 221.3 ± 0.3 189.1 ± 0.4 75.33
GSO 318 ± 1 493.6 ± 0.5 798.5 ± 0.6 188.5 ± 0.5 76.72
328 ± 1 504.3 ± 0.6 1613.6 ± 0.7 190.8 ± 0.6 75.99
Coatings 14, 7714, x FOR PEER REVIEW
2024, 2024,
Coatings 16 of 22 15 of 20

Figure
Figure 9. 9.PDP
PDPcurves
curvesfor
for C38
C38 (a)
(a) without
withoutand
and(b)
(b)with
withGSO
GSOat at
different temperatures.
different Dependence
temperatures. Dependence of
of (c) ln Icorr and (d) ln (Icorr/T) with the temperature in the absence and presence of GSO extract.
(c) ln Icorr and (d) ln (Icorr /T) with the temperature in the absence and presence of GSO extract.
Table 5. Temperature effect on electrochemical parameters.
Table 6. Thermodynamic parameters for C38 with and without GSO.
Temperature −Ecorr Icorr −βc EI
Medium
Medium (K) (mV/SCE)
∆H* (kJ/mol) (µA/cm 2)
∆S* (J/mol K) (mV/dec) (%)
Ea (kJ/mol)
298 ± 1 463.1 ± 0.5 636.1 ± 0.4 168.2 ± 0.5 -
1 M HCl 33.79 −191.53 36.38
1M HCl + GSO 308 ± 1 467.2
34.64 ± 0.2 896.4 ± 0.2
−200.87 165.1 ± 0.1 -
37.24
1M HCl
318 ± 1 470.1 ± 0.6 3428.1 ± 0.7 167.4 ± 0.6 -
328 ± 1 477.0 ± 0.8 6720.2 ± 0.7 164.3 ± 0.8 -
3.3. Microstructural Morphology
298 ± 1 465.2 ± 0.2 147.1 ± 0.3 191.7 ± 0.2 76.98
The
1 M effects
HCl + of the GSO
308 ±inhibitor
1 on the
477.4 corrosion
± 0.3 221.3behavior
± 0.3 of C38±steel
189.1 0.4 in 175.33
M hydrochlo-
ric acid GSO
were investigated by
318 ± 1 examining the
493.6 ± 0.5 surface of
798.5 ± 0.6the steel after
188.5 ± 0.5 24 h of
76.72immersion
in the acid. The metallic
328surface
±1 was observed
504.3 ± 0.6 under
1613.6 two
± 0.7 conditions:
190.8 ± 0.6in the75.99
presence and
absence of the GSO inhibitor. Without the GSO inhibitor, significant surface damage was
Table 6. Thermodynamic
observed, with cracks andparameters for C38indicating
micropores with and without GSO. pitting occurring over most of
corrosion
the surface at a uniform rate,
Medium ∆H*as (kJ/mol)
seen in Figure ∆S*
10a.(J/mol
In contrast,
K) the Esurface
a (kJ/mol)
of the steel in
the presence of
1 M HCl 0.5 g/L of GSO, as shown
33.79 in Figure 10b,
−191.53appeared smooth,36.38suggesting that
the GSO inhibitor
1 M HCl + GSO effectively prevented
34.64 the corrosion of
−200.87the C38 steel. The inhibitory
37.24 effect
of GSO can be attributed to its ability to limit the access of the corrosive electrolyte to the
surface of the steel, Morphology
3.3. Microstructural thereby reducing the rate of corrosion. The mechanism by which GSO
inhibits theeffects
The corrosion
of theofGSO
C38 steel can on
inhibitor be the
attributed
corrosionto behavior
the formation
of C38ofsteel
a protective
in 1 M layer
of hydrochloric
adsorbed molecules
acid were on the surface
investigated by of the steel.the
examining This layerofacts
surface the as a barrier
steel after 24 preventing
h of
theimmersion
corrosiveinelectrolyte from
the acid. The reaching
metallic thewas
surface underlying steel and
observed under two causing
conditions:corrosion.
in the The
protective layer is formed by the adsorption of the molecules of grape seed oil onto the
surface of the steel, and this adsorption is facilitated by the presence of the acid, confirming
its inhibitory effect. Moreover, and in order to investigate the impact of an organic layer
on the chemical composition of the surface of C38 steel, EDS (energy-dispersive X-ray
spectroscopy) analysis was conducted on both protected and unprotected samples, and the
Coatings 2024, 14, 77 16 of 20

results are presented in Figure 10c,d. The EDS analysis of the unprotected sample, shown in
Figure 10c, revealed the elemental composition of the surface of the steel, with no evidence
of any organic layer. However, in the protected sample (Figure 10d), the presence of an
organic layer was confirmed, and differences were observed in the elemental composition
of this layer. Specifically, the carbon peak in the EDS analysis corresponds to the carbon
atoms of the major components of the GSO extract, indicating that the organic layer was
formed from the GSO inhibitor. These results suggest that the formation of a stable organic
layer on the surface of C38 steel can effectively prevent corrosion phenomena [67–69]. The
proposed mechanism for the inhibitory effect of GSO on C38 steel corrosion involves the
formation of a protective organic layer on the metal surface (Figure 10e). This layer acts as a
physical barrier limiting the access of the corrosive electrolyte and preventing electrochemi-
cal reactions. The GSO extract’s active sites as well as their functional groups contribute to
Coatings 2024, 14, x FOR PEER REVIEW 18 of 22
the formation of the organic layer, which stabilizes the surface against corrosion.

Figure 10. SEM images and their corresponding EDS compositional results for (a,c) bare C38 surface
Figure 10. SEM images and their
immersed in 1 Mcorresponding EDS
HCl alone and (b,d) aftercompositional
24 h of immersionresults for +(a,c)
in 1 M HCl bare
0.5 g/L C38
GSO. (e) surface
The
immersed in 1 M HCl alone and (b,d) after 24 h of immersion in 1 M HCl + 0.5 g/L GSO. (e) The
proposed anticorrosive mechanism of GSO inhibitor on C38 surface.

proposed anticorrosive mechanism of GSO inhibitor on C38 surface.

4. Conclusions
In summary, this study focused on understanding the interaction between GSO ex-
tract and the C38 surface, with the goal of developing an organic layer that can protect
Coatings 2024, 14, 77 17 of 20

4. Conclusions
In summary, this study focused on understanding the interaction between GSO ex-
tract and the C38 surface, with the goal of developing an organic layer that can protect
metallic materials from corrosion in harsh environments. Comprehensive theoretical predic-
tion assessments were conducted before the experimental studies, indicating that specific
molecules were anticipated to exhibit a robust affinity for the C38 surface due to their
exceptional electronic and structural properties. From this perspective, electrochemical
and characterization techniques were employed to examine the corrosion inhibition perfor-
mance of GSO extract in HCl solution. Theoretical findings indicated that both LA (linoleic
acid) and OA (oleic acid) molecules, whether in parallel or perpendicular arrangements,
exhibit a propensity to interact with an Fe surface. This interaction is particularly facilitated
through the carboxyl groups, and, interestingly, the parallel orientation is energetically
favored, as evidenced by DFTB calculations. Owing to the excellent donor–acceptor charac-
teristics exhibited by both molecules and the synergistic effects resulting from inter- and
intramolecular interactions, it is conceivable that strong chemical bonds may form between
LA@OA molecules and Fe atoms, characterized by a notably higher adsorption energy
value (−6.74 eV). The experimental results clearly indicate that the inhibition efficiency of
GSO extract depends on its concentration. Notably, the findings demonstrate a remarkable
inhibition performance, reaching approximately 79% at a concentration of 0.5 g/L against
C38 corrosion. Electrochemical analyses further revealed that when compared to the blank
solution, GSO extract substantially enhanced corrosion resistance while reducing corro-
sion current density. The adsorption behavior aligns with the Langmuir isotherm model,
supporting a mode of mixed physical and chemical interactions. Through meticulous
control of concentration and temperature parameters, it is observed that the adsorption
capability of LA and OA molecules on the Fe surface is predominantly attributed to the
synergistic influence of LA@OA. This synergistic effect significantly amplifies electron
transfer and bonding interactions, consequently leading to the formation of stable inhibitor
films that offer exceptional corrosion protection. This was verified by the surface analyses.
By elucidating the interfacial mechanism of LA@OA molecules, this study has revealed
the importance of the structural design of corrosion inhibitors in effectively facilitating the
corrosion inhibition process.

Author Contributions: A.B.: investigation, formal analysis, writing–original draft; A.H.A.-M.: formal
analysis, funding acquisition, data curation; E.A.N.: formal analysis, data curation; J.M.A.-A.: formal
analysis, funding acquisition; A.A.A.-G.: data curation, funding acquisition; O.I.E.M.: formal analysis;
R.S.: formal analysis; M.C.: conceptualization, methodology, investigation, writing–original draft,
writing—review and editing; A.C.: conceptualization, investigation, methodology, writing–original
draft, writing—review and editing, supervision; Y.G.K.: funding acquisition, writing–review and
editing. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the Fundamental-Core National Project of the National Research
Foundation (NRF) funded by the Ministry of Science and ICT, Republic of Korea (2022R1F1A1072739).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All results of this study are included in the manuscript.
Conflicts of Interest: The authors declare no conflicts of interest.

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