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Coco Monoethanolamide Surfactant as a Sustainable Corrosion Inhibitor for

Mild Steel: Theoretical and Experimental Investigations

Article in Molecules · February 2023

DOI: 10.3390/molecules28041581

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 molecules
Article
Coco Monoethanolamide Surfactant as a Sustainable
Corrosion Inhibitor for Mild Steel: Theoretical and
Experimental Investigations
Richika Ganjoo 1 , Shveta Sharma 1 , Praveen K. Sharma 1 , O. Dagdag 2 , Avni Berisha 3 , Eno E. Ebenso 2, * ,
Ashish Kumar 4, * and Chandrabhan Verma 5

1 Department of Chemistry, School of Chemical Engineering and Physical Sciences, Lovely Professional
University, Phagwara 144402, India
2 Centre for Materials Science, College of Science, Engineering and Technology, University of South Africa,
Johannesburg 1710, South Africa
3 Department of Chemistry, Faculty of Natural and Mathematics Science, University of Prishtina,
10000 Prishtina, Kosovo
4 NCE, Department of Science and Technology, Government of Bihar, Patna 803108, India
5 Interdisciplinary Research Center for Advanced Materials, King Fahd University of Petroleum and Minerals,
Dhahran 31261, Saudi Arabia
* Correspondence: [email protected] (E.E.E.); [email protected] (A.K.)

Abstract: Recent studies indicate that surfactants are a relatively new and effective class of corrosion
inhibitors that almost entirely meet the criteria for a chemical to be used as an aqueous phase
corrosion inhibitor. They possess the ideal hydrophilicity to hydrophobicity ratio, which is crucial for
effective interfacial interactions. In this study, a coconut-based non-ionic surfactant, namely, coco
monoethanolamide (CMEA), was investigated for corrosion inhibition behaviour against mild steel
(MS) in 1 M HCl employing the experimental and computational techniques. The surface morphology
was studied employing the scanning electron microscope (SEM), atomic force microscope (AFM),
and contact measurements. The critical micelle concentration (CMC) was evaluated to be 0.556 mM
Citation: Ganjoo, R.; Sharma, S.;
and the surface tension corresponding to the CMC was 65.28 mN/m. CMEA manifests the best
Sharma, P.K.; Dagdag, O.; Berisha, A.;
inhibition efficiency (η%) of 99.01% at 0.6163 mM (at 60 ◦ C). CMEA performs as a mixed-type inhibitor
Ebenso, E.E.; Kumar, A.; Verma, C.
and its adsorption at the MS/1 M HCl interface followed the Langmuir isotherm. The theoretical
Coco Monoethanolamide Surfactant
findings from density functional theory (DFT), Monte Carlo (MC), and molecular dynamics (MD)
as a Sustainable Corrosion Inhibitor
for Mild Steel: Theoretical and
simulations accorded with the experimental findings. The MC simulation’s assessment of CMEA’s
Experimental Investigations. high adsorption energy (−185 Kcal/mol) proved that the CMEA efficiently and spontaneously
Molecules 2023, 28, 1581. adsorbs at the interface.
https://doi.org/10.3390/
molecules28041581 Keywords: non-ionic surfactant; coco mono ethanol amide; corrosion inhibition; electrochemical and
theoretical techniques
Academic Editor: Changjian Lin

Received: 26 December 2022

Revised: 14 January 2023
Accepted: 27 January 2023 1. Introduction
Published: 7 February 2023
The persistent and spontaneous deterioration of metal structures caused by chemical
and/or electrochemical interactions with environmental components is known as cor-
rosion. [1–3]. Failures due to corrosion have a significant impact on several businesses,
Copyright: © 2023 by the authors.
particularly those reliant on the petroleum industry where metallic materials are widely
Licensee MDPI, Basel, Switzerland. used [4,5]. The corrosion-related failures have a negative impact on the productivity and
This article is an open access article ongoing operations of these businesses. Because of the corrosion failures, various industrial
distributed under the terms and and metallurgy operations, including descaling, electrolyte-based cleaning, pickling, and
conditions of the Creative Commons acidification, cause a significant loss of metallic elements throughout the surface treat-
Attribution (CC BY) license (https:// ment [6,7]. Numerous economic and safety issues are brought on by corrosion failure.
creativecommons.org/licenses/by/ Corrosion currently costs the world economy more than USD 2.5 trillion annually [8].
4.0/). Corrosion failures have been blamed for several accidents, particularly in the petrochemical

Molecules 2023, 28, 1581. https://doi.org/10.3390/molecules28041581 https://www.mdpi.com/journal/molecules

Molecules 2023, 28, 1581 2 of 24

sector. These initiatives aim to cut the cost of corrosion by 15 to 35% which is equivalent to
USD 375 billion to USD 875 billion, respectively [8,9]. Due to growing urbanization and
industrialisation, the negative effects of corrosion, such as safety and financial penalties,
are anticipated to increase. Therefore, depending on the type of metal and electrolytes,
corrosion experts have devised numerous attempts. Every effort has advantages and disad-
vantages unique to it. Nevertheless, it has been proven that one of the best and most widely
used techniques in aqueous electrolytes is the employment of organic molecules [10–13].
Numerous organic compound families, particularly heterocycle ones, are widely used in
corrosion prevention [14–16]. But they face a problem with low solubility, particularly for
those with aromatic rings (s). Surfactants, on the other hand, are a relatively recent class
of corrosion inhibitors that have nearly all the necessary characteristics for a material to
be used as an aqueous phase corrosion inhibitor [17–20]. They have the proper ratio of
hydrophilicity (polar functional groups) to hydrophobicity (hydrocarbon chains), which is
primarily required for powerful interfacial interactions [17–20].
Surfactants have an amphiphilic structure consisting of a polar head and a nonpolar
tail. They could be bola form, Gemini-type, zwitterionic, anionic, cationic, nonionic, or
anionic, depending on the type of head. Surfactants are commonly used for lubrication,
anti-wear, degreasing, anti-scaling, and acid picking of iron and steel, as well as mineral ore
processing and acidification of oil wells. They are also extensively employed to avoid the
corrosion of metals and alloys [19,21–24]. Surfactants are a particular family of organic in-
hibitors that adsorb on metal surfaces, offering effective metal corrosion protection [25–27].
The study and synthesis of surfactants (non-ionic, anionic, cationic, and zwitterionic) as
inhibitors in diverse media have been the focus of many researchers [28–36]. In addition to
being ecologically friendly and sustainable, non-ionic surfactants also have the potential to
reduce corrosion. They have centres with a high electron density (N, S, O, P, π electrons
and aromatic ring), enabling them to adsorb on metallic surfaces and protecting them from
corrosive environments [37–40]. Some green corrosion inhibitors, according to reports, are,
however, costly or only work well when administered in high concentrations. Non-ionic
surfactants are reported to exhibit significant inhibitory efficiency for the corrosion of
metals in a variety of corrosive conditions and to have noticeably lower critical micelle con-
centrations (CMCs) than equivalent ionic surfactants [19,38,41,42]. Undoubtedly, exploring
ecological and inexpensive corrosion inhibitors for metal corrosion inhibition is significant.
Coco mono ethanol amide (CMEA) is a coconut-based surfactant, derived from the fatty
acids from coconut oil and monoethanolamine (MEA) and it is widely used in cosmetic
products and causes no harm to marine life or human safety. The structure of CMEA shows
that the nonpolar hydrophobic moiety is a long carbon chain, and the polar hydrophilic
moiety of the compound comprises readily protonated nitrogen and oxygen atoms that
provide the surfactant with a remarkable anti-corrosion potential. This research aims to
examine the mechanism of CMEA’s inhibition and its effectiveness for MS in 1 M HCl. The
findings of weight loss (WL), electrochemical impedance spectroscope (EIS), and poten-
tiodynamic polarization (PDP) to investigate the surfactant’s inhibitory performance are
presented in Sections 3.2 and 3.3, respectively, and to examine the surface characteristic of
mild steel (MS), scanning electron microscope (SEM), atomic force microscope (AFM), and
contact angle examination were carried out; the discussions are provided in Section 3.4. To
validate the experimental results and to comprehend the connection between the inhibitor
structure and MS, theoretical studies are also performed.

2. Result and Discussion

2.1. CMC Determination
The surface tension (ST) measurements were done at various doses of CMEA and the
CMC was calculated to be 0.556 mM by plotting ST against concentration (Figure 1). The
surface tension is reduced with the increase in dose and then becomes constant. The point
where the linearly dependent area’s regression straight line intersects with the straight line
 Molecules 2023, 28, x FOR PEER REVIEW 3 of 26

Molecules 2023, 28, 1581 3 of 24

surface tension is reduced with the increase in dose and then becomes constant. The point
where the linearly dependent area’s regression straight line intersects with the straight
line traversing the region of constant surface tension yields the CMC. A surface tension
traversing the region of constant surface tension yields the CMC. A surface tension reading
reading of 65.28 mN/m was recorded at the CMC.
of 65.28 mN/m was recorded at the CMC.

Figure
Figure1.1.The
Theplot of Surface
plot tension
of Surface vs. concentration.
tension vs. concentration.

2.2.WL
2.2. WLStudies
Studies
2.2.1.Impact
2.2.1. Impactof of Temperature
Temperature andand Concentration
Concentration
The
TheWL WL evaluations
evaluationswereweredone at different
done concentrations
at different at 30–60at°C30–60
concentrations ◦ C to comprehend
to comprehend
the
themode
mode of of
adsorption
adsorption(physical or chemical).
(physical The results
or chemical). Theofresults
the WLof experiments are ex‐
the WL experiments are
hibited in Table 1. It can be concluded that the values for inhibitory effectiveness
exhibited in Table 1. It can be concluded that the values for inhibitory effectiveness (WL%) (WL%)
and
andsurface
surfacecoverage
coverage (θ)(θ)
riserise
along withwith
along the concentration
the concentration of CMEA. The highest
of CMEA. The η% WL
highest η%WL
was obtained at a dose of 0.6163 mM. With the rise in temperature from 30 ℃ to 60 ◦℃, the ◦
was obtained at a dose of 0.6163 mM. With the rise in temperature from 30 C to 60 C, the
inhibition effectiveness increased and was highest at 60 ℃ and◦0.6163 mM concentration,
inhibition effectiveness increased and was highest at 60 C and 0.6163 mM concentration,
with an inhibition efficiency of 99.01%, and no increase in efficiency was seen beyond this
with an inhibition
concentration, which isefficiency
accreditedofto99.01%,
the MS’sand noareas
active increase
beingin efficiency
fully was
saturated. Theseen
in‐ beyond
this concentration, which is accredited to the MS’s active areas being
crease in the inhibition effectiveness at higher temperatures is ascribed to enhancement in fully saturated. The
increase in the inhibition effectiveness at higher temperatures is
the energy of the adsorbate molecules to cross the activation energy barrier easily and ascribed to enhancement
in thetoenergy
leads of the adsorbate
chemisorption. The corrosion rate, ν (mg.cm
molecules to cross 2 hthe activation
−1), is dependentenergy
on bothbarrier
the tem‐easily and
leads toand
perature concentration. The corrosion rate, ν (mg.cm2 h−1 ), is dependent on both the
chemisorption.
temperature and concentration.
Table 1. WL parameters for mild steel corrosion in 1 M HCl at different doses of CMEA at 30–
60℃.
Table 1. WL parameters for mild steel corrosion in 1 M HCl at different doses of CMEA at 30–60◦ C.
Temperature (°C) Conc. (mM) Weight Loss (mg) 𝝂 (mg cm−2 h−1) Surface Coverage (θ) ηWL%
Temperature (◦ C) Conc. (mM) Weight Loss (mg) Surface Coverage (θ)
Blank 55.944 0.518ν ‐ ‐ ηWL %
Blank 55.944 0.518 - -
0.2054
0.2054
23.112
23.112
0.214
0.214
0.5854
0.5854
58.54 58.54
◦C 0.3081
0.3081 16.956
16.956 0.157
0.157 0.6956
0.6956 69.56 69.56
3030 °C 0.4109 10.692 0.099 0.8075
0.4109
0.5136
10.6927.776
0.099
0.072
0.8075
0.8598
80.75 80.75
85.98
0.5136
0.6163 7.776 4.32 0.072
0.040 0.8598
0.9223 85.98 92.23
0.6163
Blank 4.32 70.95 0.040
0.657 0.9223
- 92.23 -
0.2054 28.188 0.261 0.6015 60.15
Blank
0.3081
70.95 19.44
0.657
0.180
‐
0.7253
‐ 72.53
40 ◦ C
0.2054
0.4109 28.188
11.664 0.261
0.108 0.6015
0.8345 60.15 83.45
0.5136
40 °C 0.3081
0.6163
19.447.884
3.996
0.073
0.180
0.037
0.8887
0.7253
0.9426
72.53 88.87
94.26
0.4109
Blank
11.664
80.244
0.108
0.743
0.8345
-
83.45 -
0.5136
0.2054 7.88426.028 0.073
0.241 0.8887
0.6748 88.87 67.48
0.3081 12.636 0.117 0.7617 76.17
50 ◦ C 0.4109 11.556 0.107 0.8547 85.47
0.5136 8.1 0.075 0.8987 89.87
0.6163 2.7 0.025 0.9653 96.53
Blank 88.128 0.816 - -
0.2054 26.892 0.249 0.6946 69.46
0.3081 18.684 0.173 0.7876 78.76
60 ◦ C 0.4109 11.124 0.103 0.8735 87.35
0.5136 7.236 0.067 0.9169 91.69
0.6163 0.864 0.008 0.9895 99.01
 Blank 88.128 0.816 ‐ ‐
0.2054 26.892 0.249 0.6946 69.46
0.3081 18.684 0.173 0.7876 78.76
60 °C
0.4109 11.124 0.103 0.8735 87.35
0.5136 7.236 0.067 0.9169 91.69
Molecules 2023, 28, 1581 4 of 24
0.6163 0.864 0.008 0.9895 99.01

The WL experiment results were used to plot the graphs between η%WL vs. tempera‐
The corrosion
ture and WL experiment
rate vs. results were used
concentration to plot
(Figure thegraphs
2). The graphsdemonstrate
between η%howWL vs. tem-
temper‐
perature and corrosion
ature influences rateefficiency,
inhibition vs. concentration (Figure
and also the 2). The
necessity graphs
of the demonstrate
corrosion rate. how
temperature influences inhibition efficiency, and also the necessity of the corrosion rate.

Figure 2. The
Figure 2. The impact
impact of
of concentration
concentration (Left)
(Left) and
and temperature
temperature (Right)
(Right) on
on the
the corrosion
corrosion inhibition
inhibition
potential
potential of
of CMEA
CMEA for
for MS
MS in
in 11 M
M HCl.
HCl.
2.2.2. Activation Parameters Studies
2.2.2. Activation Parameters Studies
The activation parameters like activation entropy (∆S*), activation enthalpy (∆H*), and
The activation parameters like activation entropy (∆S*), activation enthalpy (∆H*),
activation energy (Ea ) were studied for the optimum concentration of 0.6163 mM at 30, 40,
and activation energy (Ea) were studied for the optimum concentration of 0.6163 mM at
50, and 60 ◦ C to further examine the inhibition properties of CMEA and their dependence
30, 40, corrosion
on the 50, and 60rate
°C (ν
to)further examineparameters
. The activation the inhibition properties
were ofby
calculated CMEA and theirand
the Arrhenius de‐
pendence on the corrosion rate (𝜈 . The
Eyring equations given below [33,34,43,44]: activation parameters were calculated by the Ar‐
rhenius and Eyring equations given below [33,34,43,44]:
log(ν) = log A − Ea /2.303RT (1)
log 𝜈 log 𝐴 𝐸 /2.303𝑅𝑇 (1)
 ∗
∆S ∗ ∆H ∗
 
RT
ν = 𝑅𝑇exp Δ𝑆 exp − Δ𝐻 ∗ (2)
𝜈 Nh exp R exp RT (2)
𝑁ℎ 𝑅 𝑅𝑇
where v, T, h, N, A, and Ea denote the corrosion rate, temperature, Planck constant, Avo-
gadro 𝑣, T, h, Arrhenius
wherenumber, N, A, and pre-exponential
Ea denote the corrosion rate,
factor, and temperature,
corrosion Planck
activation constant,
energy, Avo‐
respectively.
gadroThenumber, Arrhenius
log v vs. pre‐exponential
1/T (Equation factor, and
(5)) and log(v/T) vs.corrosion activation
1/T (Equation energy,
(6)) were respec‐
plotted to
attain Ea and ∆S* and ∆H* values. The activation parameters obtained for 0.6163 mM CMEA
tively.
are displayed in Table 2. The ∆H* value is positive, indicating endothermic adsorption,
which means the adsorption increases with a temperature increase. The negative value of
∆S* designates a decrease in the entropy attributed to the CMEA adsorption. The Arrhenius
and Eyring plots for 0.6163 mM concentration of CMEA are exhibited in Figure 3.

2.2.3. Thermodynamic and Isotherm Studies

The adsorption isotherms at different temperatures (30–60 ◦ C) were studied to compre-
hend the metal surface and the CMEA interaction. The surface coverage (θ) data acquired
from the WL experiments were applied to various isotherms. The data fitted accurately into
the Langmuir adsorption isotherm (LAI; R2 ~1). The LAI equation is given below [45,46]:

Cinh 1
= Cinh + (3)
θ Kads

where the equilibrium adsorption constant is denoted by Kads and whose values were
derived from the straight line’s intercept, which was obtained by plotting Cinh /θ against
Cinh . The LAI at different temperatures is displayed in Figure 4.
 Molecules 2023, 28, x FOR PEER REVIEW 5 of 26

Molecules 2023, 28, 1581 The log v vs. 1/T (Equation (5)) and log(𝑣/T) vs. 1/T (Equation (6)) were plotted 5 of 24
to
attain Ea and ∆S* and ∆H* values. The activation parameters obtained for 0.6163 mM
CMEA are displayed in Table 2. The ∆H* value is positive, indicating endothermic ad‐
2. Activation
sorption,
Table parameters
which means obtained for MS
the adsorption corrosion
increases in 1aMtemperature
with HCl solution in the 0.6163
increase. mM
The CMEA.
negative
value of ∆S* designates a decrease in −the entropy attributed to the CMEA adsorption. The
Concentration (mM) Ea KJ mol 1 ∆H* KJ mol−1 ∆S* KJ.mol−1 K−1
Arrhenius and Eyring plots for 0.6163 mM concentration of CMEA are exhibited in Figure
3. 0.6163 40.83 43.85 −0.099

lecules 2023, 28, x FOR PEER REVIEW 6 of 26

Figure 3. Arrhenius
Figure 3. Arrhenius (Left)
(Left) and
and Eyring
Eyring (Right)
(Right) plots
plots for
for mild
mild steel
steel at
at 0.6163
0.6163 mM
mM dosage
dosage of
of CMEA
CMEA at
at
various temperatures in 1 M HCl.
various temperatures in 1 M HCl.

Table 2. Activation parameters obtained for MS corrosion in 1 M HCl solution in the 0.6163 mM
CMEA.

Concentration (mM) Ea KJ.mol−1 ∆H* KJ.mol−1 ∆S* KJ.mol−1.K−1

0.6163 40.83 43.85 −0.099

2.2.3. Thermodynamic and Isotherm Studies

The adsorption isotherms at different temperatures (30–60 °C) were studied to com‐
prehend the metal surface and the CMEA interaction. The surface coverage (θ data ac‐
quired from the WL experiments were applied to various isotherms. The data fitted accu‐
rately into the Langmuir adsorption isotherm (LAI; R2~1). The LAI equation is given be‐
low [45,46]:
𝐶 1
𝐶 (3)
𝜃 𝐾
where the equilibrium adsorption constant is denoted by 𝐾 and whose values were
derived from the straight line’s intercept, which was obtained by plotting Cinh/θ against
Cinh. The LAI at different temperatures is displayed in Figure 4.

Figure 4. Plots showing

Figure theshowing
4. Plots LAI for MS
the at
LAIvarying
for MSCMEA doses
at varying in 1 Mdoses
CMEA HCl. in 1 M HCl.

The value The value

of Kads of Kads
attained at attained
varying at varying
doses dosesare
of CMEA of CMEA are in
accessible accessible
Table 3. in Table 3. The
The
high kwith
high kads values ads values with the temperature
the temperature rise that
rise recommend recommend thatenergy
the binding the binding
of the energy
in‐ of the
inhibitor
hibitor increase withincrease with the temperature.
the temperature.

Table 3. Thermodynamic adsorption parameters in 1 M HCl for MS at various CMEA doses between
30 and 60 °C.

Temp. (°C) Kads × 104 (M−1)  Gads

0
KJ.mol−1 H ads
0
KJ.mol−1 Sads
0
KJ.mol−1.K−1
30 0.504 −31.59 0.140
40 0.534 −32.78 0.139
10.96
50 0.685 −34.50 0.131
60 0.720 −35.70 0.140
Molecules 2023, 28, 1581 6 of 24

Table 3. Thermodynamic adsorption parameters in 1 M HCl for MS at various CMEA doses between
30 and 60 ◦ C.

Temp. (◦ C) Kads × 104 (M−1 ) ∆G0ads KJ·mol−1 ∆H0ads KJ·mol−1 ∆S0ads KJ·mol−1 ·K−1
30 0.504 −31.59 0.140
40 0.534 −32.78 0.139
10.96
50 0.685 −34.50 0.131
60 0.720 −35.70 0.140

The ∆Gads
0 values were derived from the K
ads using Equation (8) [47,48]:

−∆G◦ ads
   
1
Kads = exp (4)
55.5 RT

The physical symbols have their standard meaning [45,46]. From Table 3, it can be
seen that the ∆Gads
0 were negative, suggesting the spontaneous reaction of the inhibitors

being adsorbed on the MS, and the values are between −30 and −40 KJ mol−1 and hence,
signify mixed adsorption, i.e., both physical (around −20 kJ mol−1 ) and chemical ad-
sorption (>−40 kJ mol−1 ); and the adsorption tends to go towards chemisorption with
increasing temperature.
The heat of the adsorption (∆Hads 0 ) value obtained from the Van ’t Hoff equation

(Equation (9)) displayed in Table 3 was positive, indicating an endothermic reaction [49,50]:

−∆H ◦ ads
log Kads = + constant (5)
2.303RT

∆Hads
0 was obtained by the slope of a straight line by plotting log k
ads vs. 1/T. The
∆S0ads values were obtained by substituting the other thermodynamic values in the basic
thermodynamic equation given below [51,52]:
◦ ◦
∆Gads = ∆Hads − T∆S◦ads (6)

The adsorption entropy (∆S0ads ) values decreased with the temperature, indicating an
enhancement in the adsorption of the inhibitor. The ∆S0ads values for the CMEA adsorption
were calculated to be positive with no discernible change at various temperatures.

2.3. Electrochemical Studies

2.3.1. Open Circuit Potential (OCP) Studies
For MS, the OCP was measured in 1 M HCl concerning time for varying concentrations
of CMEA, and the OCP for a blank solution was evaluated to be 0.432 V. The solution was
kept unstirred for 1 h and after that, the OCP was run for 500 s and a straight line parallel to
the time axis exhibited the achievement of steady-state potential. The OCP values obtained
for different concentrations with respect to time, as shown in Figure 5. The OCP values
shifted for the inhibited solution to higher negative values, demonstrating that the inhibitor
primarily adsorbs on the cathodic sites.

2.3.2. Potentiodynamic Polarization (PDP) Studies

The voltage is applied between the MS and SCE in a potentiodynamic polarisation
(PDP) experiment, and the current is monitored. The data obtained from the PDP experi-
ment were used to plot the log (i) vs. E, and the Tafel curves were obtained for MS in 1 M
HCl at 30 ◦ C for variable doses of CMEA, as shown in Figure 6. From Figure 6, it can be
concluded that the Tafel slopes at different inhibitor concentrations follow a regular trend
with decreasing corrosion current density (jcorr ). The shift towards the cathodic direction
demonstrates that the inhibition was predominantly cathodic and inhibited the hydrogen
evolution reaction. The PDP parameters, including Ecorr (corrosion potential), jcorr (current
density), ba (anodic Tafel slope), and bc (cathodic Tafel slope), are achieved by using the
 2.3. Electrochemical Studies
2.3.1. Open Circuit Potential (OCP) Studies
For MS, the OCP was measured in 1 M HCl concerning time for varying concentra‐
tions of CMEA, and the OCP for a blank solution was evaluated to be 0.432 V. The solution
Molecules 2023, 28, 1581 was kept unstirred for 1 h and after that, the OCP was run for 500 s and a straight 7 ofline
24
parallel to the time axis exhibited the achievement of steady‐state potential. The OCP val‐
ues obtained for different concentrations with respect to time, as shown in Figure 5. The
OCP values
corrosion rateshifted
analysisfor
in the
the inhibited
nova 2.1.4solution to higher
programme negativethe
to extrapolate values, demonstrating
cathodic and anodic
that the inhibitor primarily adsorbs on the cathodic sites.
regions of the Tafel curves. The results are tabulated in Table 4.

Molecules 2023, 28, x FOR PEER REVIEW 8 of 26

Table 4. PDP parameters for MS corrosion in 1 M HCl in the absence and presence of various doses
of CMEA at 30 °C.

Corrosion
Conc. jcorr (μA ‒bc Polarization
Ecorr (V) ba (V/dec) Rate ηPDP%
(mM) cm−2) (V/dec) Resistance (Ω)
(mm/yr.)
Blank −0.427 1028 0.121 0.158 28.981 11.945 ‐
0.2054 −0.462 410.24 0.133 0.150 63.608 5.6158 60.09
0.3081 −0.453 273.62 0.098 0.117 98.047 2.7611 73.38
0.4109 −0.467 142.56 0.092 0.140 169.83 1.6565 86.13
0.5136 −0.462 125.96 0.106 0.134 204.71 1.4636 87.74
. 0.6163 −0.464
OCP vs. Time plot for29.632 0.096
MS in 1 M HCl solution0.135 828.11varying doses
with and without 0.344of CMEA.
97.11
Figure 5. OCP vs. Time plot for MS in 1 M HCl solution with and without varying doses of CMEA.

2.3.2. Potentiodynamic Polarization (PDP) Studies

The voltage is applied between the MS and SCE in a potentiodynamic polarisation
(PDP) experiment, and the current is monitored. The data obtained from the PDP experi‐
ment were used to plot the log (i) vs. E, and the Tafel curves were obtained for MS in 1 M
HCl at 30 °C for variable doses of CMEA, as shown in Figure 6. From Figure 6, it can be
concluded that the Tafel slopes at different inhibitor concentrations follow a regular trend
with decreasing corrosion current density (jcorr). The shift towards the cathodic direction
demonstrates that the inhibition was predominantly cathodic and inhibited the hydrogen
evolution reaction. The PDP parameters, including Ecorr (corrosion potential), jcorr (current
density), ba (anodic Tafel slope), and bc (cathodic Tafel slope), are achieved by using the
corrosion rate analysis in the nova 2.1.4 programme to extrapolate the cathodic and anodic
regions of the Tafel curves. The results are tabulated in Table 4.

Figure 6.
Figure 6. Tafel
Tafelplots
plotsfor
formild
mildsteel
steelfor
forblank and
blank varying
and doses
varying of CMEA
doses at 30
of CMEA at°C
30in
◦ C1 in
M 1HCl.
M HCl.

4. PDP
TableAs may parameters
be noticed for MSthe
from corrosion
findingsindisplayed
1 M HCl ininthe absence
Table andthe
4, with presence
rise inofthe
various
inhib‐doses
of CMEA
itor 30 j◦corr
dose,atthe C. values dropped from 1028 to 26.632 μA cm−2 for blank to 0.6163 mM
CMEA because an adsorbed layer of CMEA developed on the MS surface. The ba and bc
both Polarization Corrosion
Conc. (mM) Ecorr (V) jcorr showed
(µA cm−2 a ) small
ba change
(V/dec) in their
−bvalues,
c (V/dec) with increasing concentration demonstrating ηPDP %
Resistance (Ω) Rate (mm/yr.)
that the corrosion kinetics was not affected by the inhibitor’s presence, but the change was
Blank −0.427 1028
predominant in the b0.121 0.158 28.981 11.945
c, suggesting the inhibition phenomena to be cathodic controlled,
-
0.2054 −0.462 410.24 0.133 0.150 63.608 5.6158 60.09
0.3081 −0.453 which273.62
was further supported
0.098 by the0.117
Ecorr values being shifted towards
98.047 2.7611a more negative
73.38
0.4109 −0.467 direction.
142.56 0.092 0.140 169.83 1.6565 86.13
0.5136 −0.462 125.96
The 0.106
Ecorr values showed a shift of0.134 204.71CMEA to be
<85 mv, signifying 1.4636 87.74
a mixed‐type inhib‐
0.6163 −0.464 29.632 0.096 0.135 828.11 0.344 97.11
itor, and it controlled both the hydrogen evolution (cathodic) and metal dissolution (an‐
odic) reaction. The inhibition efficiency ηPDP% improved from 60.09 to 97.11%. The highest
inhibition
As may efficiency was from
be noticed obtained for 0.6163
the findings mM closeintoTable
displayed the CMC of the surfactant,
4, with and
rise in the inhibitor
beyond
dose, thethat,
jcorrno moredropped
values increase from
in the1028
efficiency wasµA
to 26.632 seen, − 2
cm owing to thetosurfactant’s
for blank 0.6163 mMad‐ CMEA
sorbed layer being saturated.

2.3.3. Electrochemical Impedance Spectroscopy (EIS) Studies

The EIS experiments were executed at 30 °C to comprehend the kinetic and mecha‐
Molecules 2023, 28, 1581 8 of 24

because an adsorbed layer of CMEA developed on the MS surface. The ba and bc both
showed a small change in their values, with increasing concentration demonstrating that
the corrosion kinetics was not affected by the inhibitor’s presence, but the change was pre-
dominant in the bc , suggesting the inhibition phenomena to be cathodic controlled, which
was further supported by the Ecorr values being shifted towards a more negative direction.
The Ecorr values showed a shift of <85 mv, signifying CMEA to be a mixed-type
inhibitor, and it controlled both the hydrogen evolution (cathodic) and metal dissolution
(anodic) reaction. The inhibition efficiency ηPDP % improved from 60.09 to 97.11%. The
highest inhibition efficiency was obtained for 0.6163 mM close to the CMC of the surfactant,
and beyond that, no more increase in the efficiency was seen, owing to the surfactant’s
adsorbed layer being saturated.
Molecules 2023, 28, x FOR PEER REVIEW
2.3.3. Electrochemical Impedance Spectroscopy (EIS) Studies 9 of 26

The EIS experiments were executed at 30 ◦ C to comprehend the kinetic and mechanistic
behaviour of the electrochemical system under consideration. The Nyquist plots were
phase angle using
constructed and frequency plots (Figure
the information 8) for
from the EISblank
findings and (Figure
inhibited 7) test
andsolutions.
the Bode It was
phase
evident
angle and from the Nyquist
frequency curves that
plots (Figure the
8) for width
blank andofinhibited
the capacitive loops expanded
test solutions. as the
It was evident
inhibitor doses rose,
from the Nyquist attributed
curves that thetowidth
an improvement
of the capacitive in theloops
surface’s
expandedabsorption
as theof the in‐
inhibitor
hibitor film.attributed
doses rose, The depression in the loops was
to an improvement in thebecause
surface’s of the non‐uniformity
absorption and coarse‐
of the inhibitor film.
ness depression
The of the metalin surface and frequency
the loops was because dispersion, and also suggested
of the non-uniformity and that the MS corro‐
coarseness of the
metalwas
sion surface and frequency
controlled by the chargedispersion, and alsoThe
transfer process. suggested
shape ofthat
the the MS corrosion
impedance curveswas
did
controlled
not change,by the charge
implying that transfer
there was process. The shape
no modification of the
to the impedance
corrosion curveswith
mechanism did not
the
change, implying
inhibitor addition. that there was
Employing the no
novamodification
2.1.4 software, to the thecorrosion mechanism
most appropriate with the
electrochem‐
inhibitor
ical addition.
equivalent Employing
circuit was used thetonova 2.1.4 software,
simulate the mostasappropriate
the EIS findings revealed inelectrochemical
Figure 7, con‐
equivalent
sisting of acircuit
serieswas used to simulate
connection betweenthe theEIS findings
solution as revealed
resistance (Rsin Figure
) and 7, consisting
these impedance of
a series connection between the solution resistance
components, together with a parallel connection between (R s ) and these impedance components,
the constant phase element
together
(CPE) and with
the apolarisation
parallel connection
resistancebetween
(Rp). The theelectrochemical
constant phasecharacteristics
element (CPE) andwere
that the
polarisation
evaluated from resistance (Rp ). The
the equivalent electrochemical
circuit are outlinedcharacteristics
in Table 5. that were evaluated from
the equivalent circuit are outlined in Table 5.

Figure 7. Nyquist plots

plots for
for blank
blank and
and different
different CMEA
CMEA doses
doses at
at 30 ◦ C in 1 M HCl for MS (Left) and
30 °C
Figure 7. Nyquist in 1 M HCl for MS (Left) and
the electrical
the electrical equivalent
equivalent circuit
circuit employed
employed to
to analyse
analyse the
the EIS
EIS data.
data.
Molecules 2023, 28, 1581 9 ofand
Figure 7. Nyquist plots for blank and different CMEA doses at 30 °C in 1 M HCl for MS (Left) 24
the electrical equivalent circuit employed to analyse the EIS data.

Figure8.8. Bode
Figure Bode phase
phaseangle
angle(Left)
(Left)and
andfrequency
frequency(Right)
(Right)plots
plotsofofmild
mildsteel
steelfor
foraablank
blankand
andinhibited
inhibited
solution ◦ C in 1 M HCl.
solutionhaving
havingvarying
varyingconcentrations
concentrationsof
ofCMEA
CMEAatat30
30 °C in 1 M HCl.

Table 5. EIS variables for MS in 1 M HCl in lack and existence of CMEA at 30 ◦ C.

To take into consideration the surface inhomogeneity caused by surface roughness,
displacements, defects, and the dispersion
CPE of active areas, the CPE is utilised instead of a
Conc. (mM) Rs (Ω) Rct (Ω cm2 ) Cdl (µF cm−2 ) ηEIS%
n Y0 (µF cm−2 )
Blank 1.68 21.45 0.84 270.29 334.34 -
0.2054 5.53 63.35 0.88 336.42 317.14 66.14
0.3081 1.57 97.34 0.85 349.85 305.15 77.96
0.4109 3.17 115.31 0.77 179.16 227.64 81.39
0.5136 5.86 210.09 0.78 216.07 196.68 89.79
0.6163 7.65 758.53 0.73 225.47 181.48 97.17

To take into consideration the surface inhomogeneity caused by surface roughness,

displacements, defects, and the dispersion of active areas, the CPE is utilised instead of a
pure capacitor. Mathematically, the expression below is used to calculate the impedance of
a CPE [53,54]:
1
ZCPE = (7)
Yo ( jω )n
where j denotes an imaginary number, Y0 and n (ranges from 0 to 1) signify the constant
phase element (CPE) and phase shift, respectively, and ω represents the angular frequency.
The CPE exponent provides a measurement of the surface’s heterogeneity and has values
in the range of 0 to 1.
Double-layer capacitance (Cdl ) values were evaluated employing Equation (12) [55,56]:

1
Cdl = (8)
2π f maxR p

where f max is the frequency at which the impedance’s imaginary component has the
highest value.
Table 5 demonstrates that Rs values were quite low as compared to the charge transfer
resistance (Rct ) values, which demonstrated that the corrosion mechanism was primarily
regulated by the transfer of electrons between the MS and the defensive layer and the
resistance of the specimen to oxidation during the application of an external potential.
The acquired values of Rs indicate that the solution conductivity is decreased by the
introduction of the CMEA, which relates to increased blockage at the metal surface’s active
sites. The obtained values of Rs are greater for the solution that contains an inhibitor. It
is evident that Rct enhanced as the inhibitor dosage increased, which validated that the
inhibitor’s adsorption layer had greater corrosion resistance. The Rct values increased from
Molecules 2023, 28, 1581 10 of 24

21.45 ohm.cm2 to 758.53 ohm.cm2 for blank and 0.6163 mM inhibitor concentration. In
addition, the reduction in Cdl value was seen because of the enhancement in the width of
the double layer or drop in the local dielectric constant as a result of inhibitor adsorption
on the MS surface. This is steady with the Helmholtz model, as shown by the subsequent
equation [57,58]:
εε 0
Cdl = S (9)
δ
where the protective layer’s dielectric constant and the permittivity of free space
(8.854 × 10−14 F cm−1 ) is denoted by ε and ε 0 , δ represents the protective layer’s width and
S stands for the electrode’s surface area. In order to anticipate the dissolution process, phase
shift (n) was considered as an indicator. The steady n values demonstrated that the charge
transfer mechanism controlled the dissolution without and with various concentrations
of CMEA.
The Bode plots obtained by plotting the EIS results are presented in Figure 8 (Bode
phase angle plots) and Figure 8 (Bode impedance plot). In the Bode phase angle plot, the
phase angle was plotted against frequency to recognize the impact of frequency on the
corrosion protection and at the surface/solution interface, and it was observed that there
is just one time constant associated with the creation of an electric double layer. A basic
understanding of the inhibitory activity of the inhibitors may be acquired from the phase
angle at high frequencies. The magnitude of the capacitive electrochemical behaviour
increases with increasing negative phase angle value. The ideal capacitor has a maximum
phase angle of 90◦ at the intermediate frequency. The phase angle value is lower in the
absence of CMEA than it is in its presence (Figure 8). The rise in the maximum phase angle
with increasing inhibitor doses facilitates the additional inhibitor molecules’ adsorption on
the MS surface, hence decreasing the metal dissolution rate and enhancing its protective
qualities. The Bode impedance graphs (Figure 8) demonstrate that absolute impedance
values increased at low frequencies with an increase in inhibitor doses. This specifies that
the defensive abilities of the inhibitor increase as its concentration increases.

2.4. Surface Examination

2.4.1. SEM Examination
The formation of an adsorbed layer of surfactant was confirmed with the help of
the SEM. The MS coupons were dipped for 6 h in 1 M HCl without and with 0.6163 mM
concentration of CMEA. The results of the SEM analysis are displayed in Figure 9. The
polished MS sample showed a smooth surface (Figure 9 a) without any pits and cracks.
After 6-h immersion in 1 M HCl, the MS surface was corroded immensely and pits and
cracks were seen, as shown in Figure 9. When the MS coupon was dipped in 1 M HCl,
having 0.6163 mM CMEA for 6 h, the MS surface showed a clear smooth surface with
reduction of surface roughness owing to the formation of an inhibitor defensive barrier and
a reduced effect of the corrosive medium.

2.4.2. AFM Examination

To further study the three-dimensional topology of mild steel, AFM analysis was
performed for the metal coupons dipped in 1 M HCl for 6 h without and with 0.6163 mM
CMEA. The 3-D and 2-D images obtained are displayed in Figure 10. A polished surface
(Figure 10a,b) with average roughness (Ra ) of 7.31 nm (Table 6) was attained for the reference
MS sample. The Ra of freely corroded MS surface without CMEA after 6-h immersion time
was 327 nm (Figure 11c,d). The 3-D image (Figure 10c) clearly shows a corroded surface
with roughness and irregularities in the topography. In the presence of an inhibitor in an
acidic medium, the least surface roughness was obtained and a much smoother surface
was obtained (Figure 10e,f).
 centration of CMEA. The results of the SEM analysis are displayed in Figure 9. The pol‐
ished MS sample showed a smooth surface (Figure 9 a) without any pits and cracks. After
6‐h immersion in 1 M HCl, the MS surface was corroded immensely and pits and cracks
were seen, as shown in Figure 9. When the MS coupon was dipped in 1 M HCl, having
0.6163 mM CMEA for 6 h, the MS surface showed a clear smooth surface with reduction
Molecules 2023, 28, 1581 11 of 24
of surface roughness owing to the formation of an inhibitor defensive barrier and a re‐
duced effect of the corrosive medium.

Molecules 2023, 28, x FOR PEER REVIEW 12 of 26

surface with roughness and irregularities in the topography. In the presence of an inhibi‐
tor in an
Figure 9. acidic
SEM medium, the least surface roughness afterwas obtained
in 11and a much smoother
Figure 9. SEM photomicrographs (a) polished
photomicrographs (a) polished surface, after
surface, immersion
immersion in M HCl
M HCl for
for 66 h.
h. (b)
(b) Blank.
Blank.
surface
(c) CMEA.was obtained (Figure 10e,f).
(c) CMEA.

2.4.2. AFM Examination

To further study the three‐dimensional topology of mild steel, AFM analysis was
performed for the metal coupons dipped in 1 M HCl for 6 h without and with 0.6163 mM
CMEA. The 3‐D and 2‐D images obtained are displayed in Figure 10. A polished surface
(Figure 10a,b) with average roughness (Ra) of 7.31 nm (Table 6) was attained for the refer‐
ence MS sample. The Ra of freely corroded MS surface without CMEA after 6‐h immersion
time was 327 nm (Figure 11c,d). The 3‐D image (Figure 10c) clearly shows a corroded

Figure10.
Figure 2-Dand
10.2‐D and3‐D
3-DAFM
AFMmicrographs
micrographsfor
forMild
Mildsteel
steel(a,b).
(a,b). Polished
Polishedsample.
sample.(c,d)
(c,d)Blank
Blanksample
sample
and(e,f)
and (e,f)sample
sample++0.6163
0.6163mM
mMCMEA
CMEAin in11M
MHCl.
HCl.

Table 6. Results of CMEA-inhibited AFM investigation of MS.

Scheme Polished Sample Blank Inhibited

Average roughness (Ra ) 7.31 nm 327 nm 20.4 nm
Root mean square roughness (Rq ) 8.67 nm 478 nm 24.1 nm
Molecules 2023, 28, 1581 12 of 24
Figure 10. 2‐D and 3‐D AFM micrographs for Mild steel (a,b). Polished sample. (c,d) Blank sample
and (e,f) sample + 0.6163 mM CMEA in 1 M HCl.

Figure 11. 11.

Figure Water contact
Water angle
contact angleanalysis:
analysis:(a)(a)polished
polishedMS,
MS,(b)
(b)after
after 66 h immersion in
h immersion in11MMHCl,
HCl,(c)(c)after
after
6h6h immersion
immersion inin
1M1M HCl
HCl + +CMEA.
CMEA.

TheTheaverage roughness
average roughnessvalues andand
values rootroot
mean square
mean values
square were
values calculated
were with
calculated thethe
with
help of nano
help scope
of nano analysis;
scope 1.51.5software
analysis; softwarewas wasused.
used.The
Theinhibited
inhibited MS sample exhibited
exhibitedthe
theleast
leastaverage
averagesurface
surfaceroughness
roughnessofof20.420.4nm,
nm, which
which was
was very
very low
low as as compared
compared to the
to the blank
blank
as aasconsequence
a consequence of the
of the defensive
defensive filmfilm of CMEA
of CMEA formed
formed on the
on the MS.MS.

2.4.3. Contact Angle Investigation

The hydrophobicity of an inhibitor layer was assessed using the contact angle (CA)
experiment. After being submerged in the corrosive medium at 30 ◦ C for 6 h, the surface
contact angles of MS steel specimens were evaluated. If a water drop is more likely to
adhere to itself than to a particular surface, that surface is termed hydrophobic, and the
water drop will bead up with a CA larger than 90◦ . If a water drop prefers to adhere to a
surface more than it adheres to itself, the surface is hydrophilic, and the drop will have a
contact angle smaller than 90◦ . Figure 11 displays the water contact angle on MS surfaces.
The contact angle of the polished MS surface was measured for reference and was found
to be 100.4◦ and demonstrating hydrophobicity because of an angle greater than 90◦ . The
surface contact angle of the uninhibited specimen is only 61.40◦ owing to the existence
of hydrophilic corrosion products (Figure 11b). After adding 0.6163 mM of CMEA, the
contact angle increases to 92.6◦ (Figure 11c). The metal surface becomes hydrophobic once
the corrosion inhibitor is added, avoiding the corrosive medium’s damaging the metal.
The increase in the contact angle approves the defensive layer of CMEA formed on the
metal surface.

2.5. Theoretical Analyses

2.5.1. DFT Results
DFT studies help in considering the mode of the inhibitory effect of corrosion com-
pounds; hence, they are extensively used in corrosion research [22,59]. Utilizing these
computational methods is essential for comprehending the association between molecular
structures and protection capabilities [60]. DFT simulations have recently been carried out
to determine the adsorption mechanism based on the inhibitor molecule’s structure, the
metal, and the aggressive medium [61,62].
Figure 12 displays the optimised molecular structures, and the frontier molecular
orbitals (HOMO, LUMO, and ESP) of the CMEA inhibitor, while Table 7 includes the quan-
tum chemical indices such as EHOMO , ELUMO , ∆E, I, A, µ, χ, η, σ, ∆N, and ∆Eback-donation
derived from DFT calculations for the molecule. According to molecular orbital theory,
the orbitals that promote chemical reactions are the HOMO and LUMO, which define the
lowest energy transition. A bond is formed by the donation and acceptance of electrons
from HOMO to LUMO, respectively, where the donor and the acceptor act as a Lewis
Molecules 2023, 28, 1581 13 of 24

base and Lewis acid correspondingly. Hence, higher values of ELUMO enhance the donor
ability and lower values of ELUMO indicate higher accepter ability. The calculated EHOMO
and ELUMO values of CMEA are −7.203 and 0.414 eV, correspondingly, which indicate the
facile electron transfer from HOMO of the inhibitor to LUMO of the Fe atom and support
the chemisorption. The effectiveness of the electron transfer, chemical stability, easier
polarization, and effective polarization of the molecule was further supported by the
Molecules 2023, 28, x FOR PEER REVIEW 14 ofless
26
energy gap (∆E) as seen in Table 7.

Figure 12. HOMO, LUMO, and ESP images of CMEA with optimised structure.
Figure 12. HOMO, LUMO, and ESP images of CMEA with optimised structure.

It is recognised that the molecule is successfully adsorbed on the metal surface if it

has a contact angle of ~0° owing to the greater contact area covered by the inhibitor. As
seen, in Figure 12 the CMEA molecule has a nearly planar structure; hence, efficient ad‐
sorption is assumed due to the enhanced surface area covered in adsorption. The ESP of
the CMEA was studied to identify the electron density of the molecule and electrophilic
and nucleophilic sites in CMEA [63,64].
Figure 12 reveals that electrophilic reactivity is related to positive (blue) areas of ESP,
while nucleophilic reactivity is associated with negative (red) regions, And that the elec‐
tron‐richest regions are primarily near conjugated bonds and heteroatoms, which pro‐
motes the creation of a chelate on the MS surface by electron transfer from amide and
hydroxy groups to the “d” orbital of the Fe atom and the chemical adsorption of CMEA,
Molecules 2023, 28, 1581 14 of 24

Table 7. Theoretically evaluated quantum chemical variables of the CMEA inhibitor.

Theoretical Parameters CMEA

EHOMO −7.203
ELUMO 0.414
∆E (ELUMO − EHOMO ) 7.617
Ionization energy (I) 7.203
Electron affinity (A) −0.414
Dipole magnitude (µ) 7.459
Electronegativity (χ) 3.394
Global hardness (η) 3.808
Global softness (σ) 0.262
Fraction of transferred electrons (∆N) 0.473
∆Eback-donation −0.952

It is recognised that the molecule is successfully adsorbed on the metal surface if

it has a contact angle of ~0◦ owing to the greater contact area covered by the inhibitor.
As seen, in Figure 12 the CMEA molecule has a nearly planar structure; hence, efficient
adsorption is assumed due to the enhanced surface area covered in adsorption. The ESP of
the CMEA was studied to identify the electron density of the molecule and electrophilic
and nucleophilic sites in CMEA [63,64].
Figure 12 reveals that electrophilic reactivity is related to positive (blue) areas of ESP,
while nucleophilic reactivity is associated with negative (red) regions, And that the electron-
richest regions are primarily near conjugated bonds and heteroatoms, which promotes the
creation of a chelate on the MS surface by electron transfer from amide and hydroxy groups
to the “d” orbital of the Fe atom and the chemical adsorption of CMEA, which results in
the development of a covalent coordination bond [65,66].
Figure 12 shows that HOMO and LUMO are mostly distributed around amide
groups in CMEA molecules, suggesting the favoured locations for electrophilic attack
by metal cations on nitrogen and oxygen atoms [67–69]. Another crucial concept is the
dipole moment (µ), which measures the bond polarity and distribution of electrons in the
molecule. The dipole moment (µ) helps in determining the inhibition effects of organic
inhibitors [70,71]. In the present study, the dipole moment is 7.459 D for CMEA (Table 7),
which is higher than µH2 O (1.88 D), and indicates robust dipole–dipole interaction in
between the MS and inhibitor and also, the molecules of the inhibitor. Higher CMEA
molecule aggregation on the MS surface is favoured by the high dipole moment by the
electronic force and results in a significant inhibitory efficiency.
The charge transfer from the inhibitor to the Fe and back donation was favoured
energetically owing to the value of ∆Eback-donation < 0 and hardness > 0. The electron
transport from the CMEA to the metal surface was further reinforced by the value of
∆N > 0 and the transfer of electrons from the metal to the inhibitor occurs when ∆N < 0 [72].
Additionally, Lukovit’s finding states that the inhibitor’s inhibitory efficacy steadily rises
if ∆N < 3.6 [73]. In the present experiment, N values are > 0 and < 3.6, demonstrating
the transport of electrons from the CMEA to the MS surface. This supports CMEA’s very
acceptable inhibitory performance demonstrated via electrochemical and weight loss tests.

2.5.2. MC and MD Simulations

The MC and MD simulations were done to examine the adsorption energy distribu-
tions for the CMEA and the adsorption phenomena of the inhibitor, respectively. The MC
and MD simulation results of CMEA adsorption in the modelled corrosive medium on the
Fe surface are displayed in Figure 13. MD is often seen as a more accurate portrayal of the
dynamics of adsorption. The CMEA inhibitor takes on a flattened shape on the surface of
MS after several hundred ps of NVT simulation and is heavily adsorbed into the Fe surface
(Figure 13).
Molecules 2023,
Molecules 2023, 28,
28, 1581
x FOR PEER REVIEW 1615of
of 26
24

Figure
Figure 13.
13. MC
MC and
and MD
MD attained
attained from
from the
the adsorption
adsorption configurations
configurations of
of the
the CMEA
CMEA in
in the simulated
the simulated
corrosive media on the MS surface.
corrosive media on the MS surface.

CMEA
CMEA hadhad aa rigid
rigidstructure
structurewith
witha a–C=O
–C=Oπ π bond,
bond, andand electrons
electrons forfor
thethe vacant
vacant ironiron
“d”
“d” orbital would come from heteroatoms containing lone pairs of electrons
orbital would come from heteroatoms containing lone pairs of electrons to make coordinateto make co‐
ordinate bonds. Consequently,
bonds. Consequently, the molecule
the molecule adsorbs onadsorbs
the Feon the surface
(110) Fe (110)in surface in a planner
a planner manner
mannercould
which which could maximize
maximize the interaction
the interaction between CMEAbetween CMEA
and the MS and the MSassurface,
surface, displayedas
displayed in Figure 13.
in Figure 13.
The following Equation (14) is used to determine the adsorption energy (Eads) for the
investigated inhibitors on the surface of Fe (110) [74]:
h i
Eads = Etotal − Esur f ace+water + Einhibitor (10)

where Etotal is the system’s overall energy as a consequence of the CMEA and the metal
surface interaction; Esurface + water is the energy of the Fe (110) surface in combination
 Molecules 2023, 28, 1581 16 of 24

with water molecules before adsorption; and EInhibitor is the free energy of the CMEA,
respectively.
In MC simulation, a huge number of arbitrarily chosen mixtures of molecules and
ions are generated in a simulation box. The several configurations are examined until the
system reaches its energy equilibrium, which is shown by a smoothing of the mean average
energy profile. Figure 14a shows a characteristic energy profile for CMEA adsorption on Fe
(110) in a vacuum, which comprises average total energy, total energy, electrostatic, van
der Waals, and intramolecular energy. The results of MC simulations show that the CMEA
Molecules 2023, 28, x FOR PEER REVIEW interacts effectively with the Fe surface (Figure 14b), with −185.85 kcal/mol adsorption
17 of 26
energy (selected from the max value of P[E]) [75,76].

Figure 14. The

Figure 14. engrossment of theof
The engrossment various energyenergy
the various components throughout
components the MCthe
throughout calculations (a)
MC calculations
and (a)
distribution of the CMEA
and distribution inhibitor’s
of the CMEA adsorption
inhibitor’s energiesenergies
adsorption on the surface of iron (b).
on the surface of iron (b).

The The
following
lengthEquation (14)between
of the bond is used to determine
the Iron and the
the adsorption energywas
atoms of CMEA (Eads) for
calculated
the investigated inhibitors
using the radial on thefunction
distribution surface of Fe (110)
(RDF) [74]: of the MD trajectory. By evaluating
analysis
bond length values, the various bond types that were formed were recognized [77,78].
𝐸 𝐸 𝐸 𝐸 (1)

where Etotal is the system’s overall energy as a consequence of the CMEA and the metal
surface interaction; Esurface + water is the energy of the Fe (110) surface in combination with
water molecules before adsorption; and EInhibitor is the free energy of the CMEA, respec‐
 CMEA interacts effectively with the Fe surface (Figure 14b), with −185.85 kcal/mol adsorp‐
tion energy (selected from the max value of P[E]) [75,76].
Molecules 2023, 28, 1581 The length of the bond between the Iron and the atoms of CMEA was calculated17usingof 24
the radial distribution function (RDF) analysis of the MD trajectory. By evaluating bond
length values, the various bond types that were formed were recognized [77,78]. Peaks in
the RDF graph that arise at certain distances from the metal surface provide information
Peaks in the RDF graph that arise at certain distances from the metal surface provide
about the type of adsorption activity occurring on the metal [67,79,80]. When the peak is
information about the type of adsorption activity occurring on the metal [67,79,80]. When
present between 1 and 3.5 Å, it depicts the chemisorption mechanism, and at distances
the peak is present between 1 and 3.5 Å, it depicts the chemisorption mechanism, and
higher than 3.5 Å, it signifies physisorption. The O and A atom’s RDF peak values are shown
at distances higher than 3.5 Å, it signifies physisorption. The O and A atom’s RDF peak
in Figure 15, and the inhibitors are less than 3.5 Å away from the Fe surface (Figure 15),
values are shown in Figure 15, and the inhibitors are less than 3.5 Å away from the Fe
indicating that the interaction between Fe (110) and inhibitor is mostly chemisorption
surface (Figure 15), indicating that the interaction between Fe (110) and inhibitor is mostly
[65,81].
chemisorption [65,81].

Figure 15.RDF
Figure15. RDFOOand
andNNatoms
atomsofofthe
theCMEA
CMEAininthe
thesimulated
simulatedcorrosive
corrosivesolution
solutiononto
ontoFe
Fesurface
surface
attainedby
attained byMDMDsimulation.
simulation.

2.6.
2.6.The
TheInhibition
InhibitionMechanism
Mechanism
It is well documented that organic compounds including surfactants become effective
It is well documented that organic compounds including surfactants become effec‐
by getting adsorbed on the metal surface. In the present investigation, the outcomes of
tive by getting adsorbed on the metal surface. In the present investigation, the outcomes
different analyses suggest that CMEA adsorbs on the metal surface and builds a defensive
of different analyses suggest that CMEA adsorbs on the metal surface and builds a defen‐
layer. The adsorption of CMEA on the MS surface in 1 M HCl can be described by
sive layer. The adsorption of CMEA on the MS surface in 1 M HCl can be described by
employing the physiochemisorption mode, just as with conventional organic corrosion
employing the physiochemisorption mode, just as with conventional organic corrosion
inhibitors. As seen in Figure 16b, protonation of the heteroatoms of CMEA in the forms
inhibitors. As seen in Figure 16b, protonation of the heteroatoms of CMEA in the forms of
of >C=O (carbonyl), -OH (hydroxyl), and >NH (2◦ -amine) can occur easily in an acidic
>C=O (carbonyl), ‐OH (hydroxyl), and >NH (2°‐amine) can occur easily in an acidic solu‐
solution. Therefore, the CMEA can exit in its mon-, di-, and/or tri-protonated (cationic)
tion. Therefore, the CMEA can exit in its mon‐, di‐, and/or tri‐protonated (cationic) forms
forms in 1 M HCl medium. As opposed to that, the build-up of counterions causes
in 1 M HCl medium. As opposed to that, the build‐up of counterions causes the metallic
the metallic surface to develop a negative charge (hydroxide and chloride ions) [82,83].
surface to develop a negative charge (hydroxide and chloride ions) [82,83]. Through phy‐
Through physisorption, these diametrically opposed charged moieties are attracted to one
sisorption, these diametrically
another. Therefore, opposed CMEA
interactions between charged andmoieties
the MSare attracted
surface in an to one solution
acidic another.
Therefore, interactions
may begin with physisorption.between CMEA and the MS surface in an acidic solution may begin
withHowever,
physisorption.
the outcomes of the present study suggest that chemisorption is the true
However,
mechanism of CMEA the outcomes of the
adsorption. Thispresent studyfrom
could result suggest that chemisorption
heteroatoms is the
deprotonating true
as they
mechanism of CMEA adsorption. This could result from heteroatoms deprotonating
approach a metallic surface by taking in electrons. Therefore, through a process known as as
they approach a metallic surface by taking in electrons. Therefore, through
donation or transfer, heteroatoms (N and O) move their unshared electron pairs to metallic a process
d-orbitals. Additionally, because metals (in this example, iron) are already electron-rich
species, this form of charge transfer results in an interelectronic repulsion state [82,83]. This
causes the iron to donate its additional electron through a mechanism known as retro- or
back-donation to the empty p-orbitals of C, O, and N. There is a noticeable relationship
between the extent of the donation and the extent of the retrodonation, and this relationship
 known as donation or transfer, heteroatoms (N and O) move their unshared electron pairs
to metallic d‐orbitals. Additionally, because metals (in this example, iron) are already elec‐
tron‐rich species, this form of charge transfer results in an interelectronic repulsion state
Molecules 2023, 28, 1581 18 of 24
[82,83]. This causes the iron to donate its additional electron through a mechanism known
as retro‐ or back‐donation to the empty p‐orbitals of C, O, and N. There is a noticeable
relationship between the extent of the donation and the extent of the retrodonation, and
is known
this as synergism
relationship [82,83].
is known The mechanism
as synergism of corrosion
[82,83]. inhibition
The mechanism of and modesinhibition
corrosion of CMEA
adsorption on the MS surface in 1 M HCl are presented in Figure 16.
and modes of CMEA adsorption on the MS surface in 1 M HCl are presented in Figure 16.

Figure 16. (a) The mechanism of corrosion inhibition. (b) Physisorption and chemisorption
chemisorption and
and (c)
Protonation of different functional groups in 1 M HCl.
Protonation of different functional groups in 1 M HCl.

3. Experimental
3.1. Specimen, Reagents
3.1. Specimen, Reagents and
and Materials
Materials
The
The MS
MS coupons
coupons were
were acquired
acquired from
from JKJK steel
steel companies (located in
companies (located in Punjab,
Punjab, India)
India)
with
with chemical composition C‐2.83%, Si‐0.38%, P‐0.02%, V‐0.27%, Mn‐0.47%, and the rest
chemical composition C-2.83%, Si-0.38%, P-0.02%, V-0.27%, Mn-0.47%, and the rest
was Fe. Coco mono ethanol amide (Figure 17) was purchased from BLD
was Fe. Coco mono ethanol amide (Figure 17) was purchased from BLD pharma, India. pharma, India.
Coco monoethanolamide (CMEA) is a non-ionic and waxy surfactant. CMEA contains the
Coco monoethanolamide (CMEA) is a non‐ionic and waxy surfactant. CMEA contains the
minimum amount of free amine and is typically used in formulations that are pH-sensitive.
minimum amount of free amine and is typically used in formulations that are pH‐sensi‐
CMEA is well recognized for its well-known moisturizer effect on finished goods. This
tive. CMEA is well recognized for its well‐known moisturizer effect on finished goods.
product is also known to contain and make excellent use of a superb emulsifier, thickening,
This product is also known to contain and make excellent use of a superb emulsifier, thick‐
and wetting ingredient. Additionally, it has significant oil solubility and good oil emulsifier
ening, and wetting ingredient. Additionally, it has significant oil solubility and good oil
qualities. CMEA can also be used as a stabilizer and foam booster. CMEA modifies the
emulsifier qualities. CMEA can also be used as a stabilizer and foam booster. CMEA mod‐
structure of foam to produce richer, denser foam. It is excellent for shampoo, shaving
ifies the structure of foam to produce richer, denser foam. It is excellent for shampoo,
cream, and liquid soap formulations when used as a viscosity controller. The electrolyte
shaving cream, and liquid soap formulations when used as a viscosity controller. The elec‐
(HCl 37%), acetone, and ethanol were procured from Sigma Aldrich. The coupons to be
trolyte (HCl 37%), acetone, and ethanol were procured from Sigma Aldrich. The coupons
used for weight loss measurements were carved into dimensions (4.5 cm × 4 cm × 0.2 cm)
to be used for weight loss measurements were carved into dimensions (4.5 cm × 4 cm × 0.2
and were grazed with emery paper of diverse grades (180 to 2200) to attain a smooth and
cm) and
glass wereand
surface grazed withwith
cleaned emery paperwater
purified of diverse grades
and dried (180undergoing
before to 2200) to attain a smooth
the experiment.
and glass surface and cleaned with purified water and dried before 2 undergoing
For the electrochemical experiment, a 5.5 cm long MS rod having a 1 cm uncovered area the
was applied.
Molecules 2023, 28, x FOR PEER REVIEW 20 of 26

Molecules 2023, 28, 1581 19 of 24

experiment. For the electrochemical experiment, a 5.5 cm long MS rod having a 1 cm2
uncovered area was applied.

Figure
Figure 17.
17. Molecular
Molecular structure
structure of
of coco
coco mono
mono ethanol amide (CMEA).
ethanol amide (CMEA).

Surface Tension Measurement

3.2. Surface
CMEA at
The surface tensions of CMEA at critical
critical micelle
micelle concentration
concentration (CMC)
(CMC) were
were measured
measured
using a Kruss K9 tensiometer with a thermostable vessel holder at 25 ± 0.1 ◦ C using the
thermostable holder at 25 ± °C
Platinum ring detachment technique.

3.3. Weight
3.3. Weight Loss
Loss Investigations
Investigations
The WL
WL study
study was
was done
done atat four ◦ C) on MS coupons
The four different
different temperatures
temperatures (30–60
(30–60 °C) on MS coupons
having an 2
having an 18
18cmcm2area.
area.The
Thecoupons
couponswere
weregrazed
grazed with emery
with emerypapers to remove
papers any any
to remove dirt dirt
and
scales present and then splashed with distilled water, acetone, and ethanol
and scales present and then splashed with distilled water, acetone, and ethanol and and weighed
after drying.
weighed afterThe samples
drying. Theafter weighing
samples afterwere submerged
weighing in the test solution
were submerged contained
in the test solutionin
six beakers, i.e., 150 mL of 1 M HCl (Blank) and five with different inhibitor concentrations
contained in six beakers, i.e., 150 mL of 1 M HCl (Blank) and five with different inhibitor
0.2054 mM, 0.3081 mM, 0.4109 mM, 0.5136 mM, 0.6163 mM added to the test solution for
concentrations 0.2054 mM, 0.3081 mM, 0.4109 mM, 0.5136 mM, 0.6163 mM added to the
6 h at 30–60 ◦ C temperature. The temperature was regulated with the help of an oven.
test solution for 6 h at 30–60 °C temperature. The temperature was regulated with the help
After immersion in the different experimental solutions for 6 h, the MS specimens were
of an oven. After immersion in the different experimental solutions for 6 h, the MS speci‐
taken out of the beakers and then cleaned and washed with water acetone and dried with a
mens were taken out of the beakers and then cleaned and washed with water acetone and
hot air blower. The weight loss of the coupons was measured accurately thereafter. The
dried with a hot air blower. The weight loss of the coupons was measured accurately
corrosion rate (ν, mg cm2 h−1 ) and inhibition effectiveness (ηwL %) was evaluated by the
thereafter. The corrosion rate (𝜈, mg cm2 h−1) and inhibition effectiveness (𝜂 % was eval‐
Equations (1) and (2), respectively [58,84]:
uated by the Equations (1) and (2), respectively [58,84]:
W0 − W𝑊
ν= 𝑊 (11)
𝜈 At (12)
𝐴𝑡
%) = 𝜈
ν0 − ν 𝜈
× 100
𝜂ηWL (% ν0 100 (12)
(12)
𝜈
where W0 and W denote the WL earlier and after dipping in a corrosive medium, respec-
tively; νW
where and W denote the WL earlier and after dipping in a corrosive medium, re‐
0 and ν signify the corrosion rate of the blank specimen and the corrosion rate in
spectively;
the inhibitor’s and 𝜈 signify
𝜈 presence, the corrosion rate of the blank specimen and the corrosion
correspondingly.
rate in the inhibitor’s presence, correspondingly.
3.4. Electrochemical Techniques
A typical three-electrode 1 L corrosion cell of Autolab PGSTAT204 equipment, 302N
model with a FRA32M impedance analyser, was employed to perform the PDP and EIS
experiments. An inbuilt nova software 2.1.4 version was utilized to calculate the electro-
chemical parameters. The test solution having an MS rod (1 cm2 exposed area) dipped
in it as a working electrode was kept for 1 h initially to attain steady-state equilibrium
potential, i.e., open circuit potential (OCP). The unstirred test solution’s OCP was then
scrutinized as a function of time till a straight line parallel to the X-axis was attained that
validated the achievement of steady-state potential. After the OCP was attained, the PDP
experiment was run under a potential range of −0.25 to + 0.25 V at a scan rate of 0.001 V/s.
The inhibition efficacy (ηPDP %) of the PDP experiment was evaluated by the Equation (3)
as follows [85]:
j0 − jcorr
ηPDP (%) = corr 0 × 100 (13)
jcorr
where the corrosion current densities in the absence and presence of inhibitor are denoted
0
by jcorr and jcorr , correspondingly.
Molecules 2023, 28, 1581 20 of 24

The EIS experiments were executed at 30 ± 2 ◦ C in a 0.01 Hz to 105 Hz frequency range

and 0.01 V amplitude of sinusoidal potential perturbation. The inhibition effectiveness
from the EIS experiment was estimated from Equation (4) given below [85]:
◦
Rct − Rct
ηeis % = × 100 (14)
Rct
◦
Rct and Rct signify the charge transfer resistances for the blank and inhibited solutions,
respectively.

3.5. Surface Morphology Study

The AFM, SEM, and contact angle analyses were done to approve the development
of the adsorbed inhibitor layer on the metal surface by using the equipment Bruker multi-
mode 8 (tapping mode with Nano Scope 1.5 software), JEOL JSM-7610F with EDS: INCA,
OXFORD, and DSA100 Drop Shape Analyzer, respectively.

3.6. Theoretical Study

Density functional theory (DFT) and Monte Carlo (MC) simulations were performed
on CMEA to further validate the findings obtained via the experiment. The DFT calcula-
tions were executed employing the Dmol3 (B3LYP/ DND/ COSMO (water) model) module
incorporated into the Biovia Materials studio programme [64,86,87]. MC and MD simula-
tions were achieved to study the adsorption behaviour and interaction between the CMEA
and the Fe (110) surface employing “Materials Studio 8.0,” advanced by Accelrys, Inc. A
three-dimensional box (27.306127, 27.306127, 20.29536) with periodic boundary conditions
was used for the simulation procedure to mimic the representative portion of the interface
free from any extraneous border impact. Before the simulation, the Fe (110) plane was
split from the iron crystal and the surface was modified. A supercell was developed by
extending Fe (110). There was constructed a 40-vacuum layer above the Fe (110) plane.
CMEA molecules were also optimized. The adsorption of CMEA on Fe (110) was simulated
at 298 K using Andersen’s thermostat, NVT, a simulation duration, and a time step of 0.8 ns
and 1 fs, respectively.

4. Conclusions
The corrosion inhibition behaviour of coco monoethanolamide (CMEA), a non-ionic
surfactant based on coconut, against MS in 1 M HCl was examined utilizing both experi-
mental and computational methodologies. The CMEA displayed an excellent inhibition
efficacy of 97.17% at 0.6163 mM concentration of CMEA, which was close to the CMC
value (0.556 mM). No further increase in the inhibition efficiency was seen beyond this
concentration attributable to the saturation of the adsorbed inhibitor layer on the MS.
The weight loss results were in accordance with the EIS and PDP results. The impact of
temperature was examined by a WL experiment and an improvement in the inhibition
effectiveness was seen with the increase in temperature depicting chemisorption. At 60 ◦ C,
the maximum inhibition effectiveness of the order of 99% was obtained at 0.6163 mM. The
adsorption isotherm that fitted was the Langmuir isotherm. From the PDP outcomes, it was
evident that the CMEA was a mixed inhibitor and predominantly controlled the hydrogen
evolution (cathodic) reaction, as was clear from the shift in Ecorr values (<85 mV). The Rct
values increased from 21.45 to 758.53 ohm cm2 owing to the development of an adsorbed
layer of surfactant that controlled the charge transfer process. The creation of a defensive
layer was validated by the SEM and AFM micrographs that depicted smooth surfaces
for inhibited coupons. From the DFT studies, the energy gap value between EHOMO and
ELUMO was evaluated to be 7.617 eV, which supported the facile electron transfer from
EHOMO of the inhibitor to ELUMO of the MS. From the MD trajectory’s RDF results, the bond
length between the inhibitor heteroatoms and Fe was less than 3.5 Å, which confirmed
the inhibitor’s chemisorption behaviour. Hence, CMEA was confirmed to be a potent
corrosion inhibitor.
Molecules 2023, 28, 1581 21 of 24

Author Contributions: Writing—original draft preparation, R.G.; writing—review and editing, A.K.
and C.V.; methodology, R.G., S.S. and P.K.S.; software, O.D., A.B., E.E.E.; supervision, A.K. and C.V.
All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The authors confirm that the data supporting the findings of this study
are available within the article.
Conflicts of Interest: The authors declare that they are clear of any financial or personal conflicts that
may have seemed to affect the research described in this paper.
Sample Availability: Samples of the compounds are available from the authors.

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