Journal of Physics and Chemistry of Solids 165 (2022) 110690

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Journal of Physics and Chemistry of Solids

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

Adsorption, corrosion inhibition mechanism, and computational studies of

Azadirachta indica extract for protecting mild steel: Sustainable and
green approach
Harish Kumar a, *, Vikas Yadav b, Anu Kumari c
a
Dept. of Chem., School of Basic Sci., Central University of Haryana, Mohindergarh, India
b
Dept. of Chem., CDL University, Sirsa, Haryana, India
c
Dept. of Chem., Jaipur National University, Jaipur, India

A R T I C L E I N F O A B S T R A C T

Keywords: The extract of Azadirachta indica (AI) leaves has been explored as a green inhibitor for mild steel (MS) in 5.0 M
Azadirachta indica hydrochloric acid by computational (DFT, Langmuir/Freundlich adsorption, frontier molecular orbital, and
DFT molecular dynamics simulation) and experimental (polarization, gravimetric, gasometric, and impedance)
Green corrosion inhibitor
techniques. Corroded surfaces have been investigated by metallurgical microscopy and SEM techniques. The
Impedance spectroscopy
Mild steel
impedance parameters and inhibition efficiency were found to increase with AI extract concentration, the latter
Molecular dynamics simulation from 50.64% to 89.25%. Various theoretical parameters, such as electronic charge in the HOMO/LUMO, Fukui
function, metal− inhibitor interaction energy (− 22.12 kJ/mol), adsorption energy (7.86 kJ/mol), back-donation
energy, chemical potential (3.95 eV), and global hardness (1.75 eV), imply high adsorption of AI extract
(flavonoid as major constituent) on MS. SEM and metallurgical imaging techniques have proved the growth of a
uniform barrier film on the surface of MS with increasing AI extract concentration. The numbers and intensities
of pits and cracks decrease with increasing AI extract concentration. A maximum of 89.25% inhibitory efficiency
was shown by AI. Wastewater from gravimetric experiments was examined for biocompatibility and biode­
gradability, and was found within the permissible range.

1. Introduction
Corrosion is a very serious problem and can lead to failure of ma­
chine parts, sometimes resulting in fatal accidents. Mild steel (MS) is
widely used in industrial and domestic appliances due to its remarkable
properties, such as high mechanical strength, cost-effectiveness, and
ease of moldability [1,2]. Dilute HCl (5.0 M) is widely used in various
industrial processes, such as acid cleaning/descaling of the inner sur­
faces of blocked pipelines, boilers, and heat exchangers, chemical
manufacturing processes, the petroleum industry, and so on [3,4].
Various corrosion protection techniques are available, but the use of
inhibitors remains the most common technique [5–9]. Most corrosion
inhibitors are organic compounds possessing one or more heteroatoms,
such as O, N, or S, or conjugated systems [10]. Many synthetic
compounds show high inhibition efficiency, but the majority of them are
toxic [11]. Natural product extracts, such as plant and their products,
are viewed as an incredibly rich source of naturally occurring chemical
compounds that can be extracted by simple procedures with low cost
and are biodegradable [12,13]. The use of these natural products, such
as those extracted from leaves, flowers, seeds, roots, and fruits, as
corrosion inhibitors has recently been reported by several authors
[14–18]. Sethuraman et al. [14] studied the anti-corrosive properties of
an extract of black pepper on MS in 1 M acid media. Okafor [15] studied
the inhibitory actions of extracts from the leaves and seeds of Phyllanthus
amarus, individually and in combination, on MS in hydrochloric and
sulfuric acids. Abdel-Gaber et al. [16] studied the inhibitory effect of
lupine (Lupinus albus L.) extract on the corrosion of steel in 1 M sulfuric
and hydrochloric acids. The anticorrosive properties of an extract of

Abbreviations: AI, Azadirachta indica; DFT, Density Functional Theory; MS, Mild Steel; HOMO, Highest Occupied Molecular Orbital; LUMO, Lowest Occupied
Molecular Orbital; CIE, Corrosion Inhibition Efficiency; FMO, Frontier Molecular Orbital; MD, Molecular Dynamics; MIT, Metallurgical Imaging Technique; GI, Green
Inhibitor; OCP, Open Circuit Potential; CR, Corrosion Rate.
* Corresponding author.
E-mail address: harishkumar@cuh.ac.in (H. Kumar).

https://doi.org/10.1016/j.jpcs.2022.110690
Received 28 October 2021; Received in revised form 8 March 2022; Accepted 8 March 2022
Available online 12 March 2022
0022-3697/© 2022 Elsevier Ltd. All rights reserved.
H. Kumar et al.
Fig. 1. Theoretical (A) and experimental (B) FTIR spectra of Flavonoid molecule.
Fig. 2. NMR spectra of Flavanone molecule observed from Magritek (Spinsolve 80) 1H-NMR.
neem leaves in 1 M nitric acid towards copper metal at three different
temperatures have been reported by Patel and Vashi [17], whereby a
98% corrosion inhibition efficiency (CIE) was achieved. Takola and
Gupta investigated the anticorrosive properties of an extract of neem
leaves towards zinc metal in a medium of sulfuric acid by a gravimetric
method [18]. A maximum CIE of 83.5% was observed for zinc metal in 2
N sulfuric acid. Extracts of the leaves, roots, and seeds of neem have been
explored as green inhibitors (GIs) for MS in 2 N sulfuric acid [19]. The
order of inhibition efficiency was seeds > roots > leaves. Up to 81% CIE
was observed by applying the seed extract. Sharma et al. have reported
the CIE of neem leaf extracts for zinc metal in sulfuric acid, as deter­
mined by a gravimetric method at different temperatures [20]. The
neem tree is known for its various medicinal benefits, and is widely
found in India, Nepal, Bangladesh, Pakistan, Sri Lanka, and the tropical
region of Asia. Recently, the United Nations has declared the neem tree
as the “Tree of the 21st Century”. In India, it is popularly called the
“divine tree”, “village pharmacy”, or “life-giving tree” [21,22]. The
major chemical constituents present in the mature leaf of Azadirachta
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Journal of Physics and Chemistry of Solids 165 (2022) 110690
indica (AI) are nimbin (a flavonoid), ascorbic acid, n-hexacosanol and its
amino acid, 7-diacetyl-7-benzoyl azadiradione, and nimbiol [23–25].
Although electrochemical methods, such as polarization and
impedance spectroscopy supported by gravimetric and gasometric
methods, provide extensive information about the corrosion inhibition
imparted by different types of inhibitors, for a full understanding of the
actual behavior of inhibitors on the MS/HCl interface, theoretical
studies, such as by density functional theory (DFT), molecular dynamics
(MD) simulation, frontier molecular orbital (FMO) calculations, and
adsorption isotherms, can provide valuable insight [26–28]. Indeed,
these theoretical techniques provide information regarding the orien­
tation, distribution, and structural arrangement of atoms on the surfaces
of metals. This should assist the design of new corrosion inhibitors for
metals and alloys in different acidic media [29–31]. Previous studies in
this context have concerned the corrosion inhibition properties of 1-ben­
zylimidazole [32] and cyclohexylamine [33] towards MS in 0.1 N sul­
furic acid, of 3,3′ -diaminodipropylamine towards carbon steel (CS) in
2.0 N hydrochloric acid [34], of trisodium phosphate towards MS in 0.1 N
H. Kumar et al.
Fig. 3. Corrosion inhibition efficiency (%) at different concentration of Azar­
dirachta indica (AI) extract observed by gravimetric technique.
Fig. 4. Variation of OCP with time for mild steel exposed to 5 M HCl solution in
absence and presence of different concentration of Azardirachta indica (AI).
sulfuric acid [35], of Agaricus bisporus as a GI for MS in 5.0 M hydro­
chloric acid [36], of hexamine towards MS in 0.1 N sulfuric acid [37], of
Musa acuminate as a GI for MS in 5.0 M hydrochloric acid [38], and of
cetyl trimethylammonium bromide towards MS in sulfuric acid [39].
From this literature survey, it became apparent that no author has
completely explained the mechanism of corrosion and adsorption of GIs
(plant-product-based) for MS in 5.0 M hydrochloric acid by combining
computational, surface (Langmuir and metallurgical imaging), and
experimental methods.
The present study focuses on the adsorption and corrosion inhibition
mechanism of AI leaf extract for protecting the surface of MS in 5.0 M
HCl, as assessed by gravimetric, gasometric, cathodic/anodic polariza­
tion, and impedance spectroscopic techniques. Surface studies based on
adsorption isotherms, SEM, and the metallurgical imaging technique
(MIT) have been used to investigate the severity of corrosion on MS. The
results of these experimental studies are supported by those of theoret­
ical (DFT) and surface (Langmuir isotherm) studies.
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Journal of Physics and Chemistry of Solids 165 (2022) 110690
Fig. 5. Polarization curves of mild steel as working electrode when exposed to
5 M HCl at room temperature at different concentration of Azardirachta indica
(AI) extract as environment friendly corrosion inhibitor. All the potentials were
measured with reference to Ag/AgCl reference electrode.
2. Materials and methods
2.1. Preparation of the AI extract
The corroding solution was prepared from deionized H2O and HCl
(Aldrich, 99.999%, 37 wt%, AR). Green leaves of the AI plant were
obtained from CDL University, Sirsa (Haryana), India. The mature green
leaves were wiped with a moist cotton cloth, left exposed to the sun, and
dried at 50 ◦ C for 24 h. The dried leaves were crushed to a fine powder
with a mortar and pestle and stored for further use as a GI for MS in 5.0 M
HCl.
2.2. Gravimetric method
MS (IS2062 Fe350) coupons, with the percentage composition Mn =
0.51, Cr = 0.14, C = 0.19, Ni = 0.09, Si = 0.17, P = 0.044, Cu = 0.06, S
= 0.057, Mo = 0.02, V < 0.02, Fe = balance, were used for corrosion
experiments. MS coupons of dimensions 1.5 × 3.0 × 0.1 cm3 were cut
from an MS sheet and successively polished with sandpaper of 100–1000
μ grade. The change in weight of the MS coupons before and after im­
mersion in 5.0 M hydrochloric acid (200 mL) for 3 h at 298 K was
recorded. The corrosion rate (CR) and CIE were determined by the ASTM
standard test procedure (D2688) according to Eqs. (1) and (2) [40]:
CR ​ (mills ​ per ​ year) ​ =
534 × Change in weight
(1)
Density × Area × time
CIE ​ = ​
(CRBlank − CRInhibitor )
× 100 (2)
CRBlank
where CRBlank and CRInhibitor are the CR in the absence and presence of
the AI extract.
2.3. Polarization study
MS of dimensions 5 × 1 cm2 was selected as the working electrode.
Only 1 cm2 of the working electrode area i.e., from top (for making an
electrical connection) and bottom (for corrosion study) was exposed.
The rest of the area was covered with epoxy resin. The MS electrode was
polarized by means of a PGSTAT 128 N potentiostat (Metrohm). Before
each polarization, the MS electrode was kept in 5.0 M hydrochloric acid
for 1 h until the attainment of constant Open-Circuit Potential (OCP).
H. Kumar et al.
Fig. 6. Nyquist plots (EIS) of mild steel immersed in 5 M HCl in absence and presence of different concentrations of Azadirachta indica (AI) at 298 K.
Fig. 7. Bode plots (A) and Randle equivalent circuit (B) of mild steel exposed to
5 M HCl solution. CPE represent constant phase element, WE represent working
electrode, Rs represent solution resistance and Rct represent charge trans­
fer resistance.
The potential of the MS electrode was measured against an Ag/AgCl
electrode. Cathodic and anodic polarization of the MS electrode was
performed at a constant temperature of 298 K. Polarization of the MS
working electrode was performed from − 200 mV to +450 mV with
respect to the OCP at a scanning rate of 0.01 V/s. The CR and CIE were
calculated from the polarization measurements by the ASTM procedure
(G61) according to Eqs. (3) and (4) [41].
The CR was calculated from the Stern− Geary equation, Eq. (3):
CR ​ (mpy) ​ = ​
0.128 × ICorr. × Eq. Wt.
(3)
Density
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Journal of Physics and Chemistry of Solids 165 (2022) 110690
The CIE was calculated according to Eq. (4):
CR(Blank) − CR(Inhibitor)
CIE ​ = ​ × 100 (4)
CR(Blank)
2.4. Impedance study
The impedance technique was applied after attaining the OCP to
study behavior at the metal− solution interface. The electrochemical
response of the interface to AC excitation frequencies from 10 kHz to 0.1
Hz was monitored. The Nyquist, Bode, and Randles equivalent circuit
models were employed to study the nature and composition of the MS/
AI interface. The CIE was calculated from the double-layer capacitance
(Cdl) according to Eq. (5) [42].
Cdl (Blank) − Cdl (Inhibitor)
CIE = × 100 (5)
Cdl (Blank)
2.5. Gasometric study
Although gravimetric, polarization, and impedance techniques pro­
vide reliable CR and CIE results, these techniques were supplemented by
a gasometric technique, whereby the rate of evolution of gas as a
cathodic by-product is directly related to the rate of electrochemical
corrosion. The principle of the gasometric method is based on mea­
surement of the volume of gas produced during the cathodic reaction of
electrochemical corrosion. The amount of gas released is directly pro­
portional to the rate of corrosion. The volume of gas evolved with
respect to time was measured from the slope of a volume versus time
graph (RVh). The degree of surface coverage and the CIE for AI were
determined from the RVh in presence and absence of AI extract (con­
centration range 0–4 g/L).
2.6. Surface study
After gravimetric study at different concentrations of AI in 5 M hy­
drochloric acid at 298 K, MS specimens were examined by SEM and MIT.
MIT gives information on the corroded specimens in the μm range,
whereas SEM provides surface information in the nm range. Surface
parameters, such as percentage porosity (PP), length of pores (LP), and
thickness of coating (TC), were determined by MIT. Metallurgical im­
aging was performed with a Kyowa− Getner set-up, running Meta-plus
software. TC (μm) and PP were recorded with Meta-plus software. The
morphologies of MS specimens after gravimetric experiments were
examined by SEM to identify the nature and type of corrosion, and the
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

Fig. 8. Trinocular inverted metallurgical micrographs of mild steel samples with and without Azadirachta indica (AI) as environment friendly corrosion inhibitor at
different concentrations.

5
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

Fig. 9. SEM image of mild steel samples blank and in presence of different concentration of Azardirachta indica (AI).

number and intensity of pits and cracks formed in blank and AI-treated
(I + A)
MS coupons. Langmuir and Freundlich adsorption isotherm (LAI and ϰ= (6)
2
FAI) studies yielded adsorption parameters such as Kads, ΔGads, activa­
tion energy (Ea), and enthalpy change (ΔH) during the adsorption Hardness,
process.
(I − A)
η= (7)
2
2.7. Theoretical study
Softness,
Theoretical studies were performed with the Gaussian 09W and 1 2
BIOVIA Material Studio (BMS) program suites to investigate the σ= = (8)
η (I − A)
adsorption mode and inhibition mechanism of AI extract. The results of
theoretical studies were correlated with the experimental data. MD Fraction of electron shifted,
simulation was performed by selecting an aqueous medium in which (χ Fe − χ Inh )
flavonoid molecules would be protonated. The theoretical parameters ΔN = (9)
2 × (ηFe − ηInh )
were estimated by Koopman’s theorem [Eqs. (6)− (9)] [43,44].
Electrochemical potential, Standard values of χ Fe and χ Inh were assumed [45].
The energy of the adsorption process, EAd was obtained from Eq.

6
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

(10).
Es− x − (Es + Ex )
EAd = (10)
n
Computational data were recorded with reference to Eqs. (11)− (18).
Electrophilicity,

μ2
ω= (11)
2η
Charge transfer max.,
I+A
ΔNMax. = (12)
2(I − A)
Adsorption energy,
Es− x − (Es + Ex )
EAd = (13)
n
Electron-releasing ability,
( )
I + 3A2
ω+ = (14)
16(I − A)
Electron-accepting ability,
( )
3I + A2
ω− = (15)
16(I − A)
Work function,

(φFe − χ Inhib )2
Δφ = − (16)
4(ηFe + ηInhib )
Back-donation energy,
η
ΔεBD = − (17)
4
Proton affinity,
( )
PA ​ = Epro − Enon pro + EH+ (18)

The theoretical study was correlated with Langmuir and Freundlich

isotherm studies [46,47]. A DFT study was performed after geometry
Fig. 10. LAI (A) and FAI (B) for Flavonoid adsorbed over the surface of MS (4.0 optimization of the flavonoid molecule employing the B3LYP functional.
g/L). The effect of solvent was also investigated. The COSMO model was used
to treat water as a uniform layer of high dielectric constant. The reac­
tivity of flavonoid molecules on the Fe (110) surface was investigated by

Fig. 11. Geometry optimized structure of flavonoid, van der Waal surfaces per atoms and Electron density distribution per atom (clockwise).

7
H. Kumar et al.
Fig. 12. Geometry optimized structure (A), LUMO (B) and HOMO (C) of Flavonoid molecule (Clockwise).
the Fukui function as implemented in the Dmol3 module of BMS soft­
ware. The Fukui function helps to determine the sites of electrophilic,
nucleophilic, and radical attack on the Fe (110) surface of MS. The Fukui
function is expressed in terms of the change in electron density with the
number of electrons at an externally applied potential. Here, the Fukui
function was expressed through a definite difference approximation
based on Hirshfeld population analysis (HPA). The adsorption of
flavonoid molecules on the Fe (110) surface was studied using the
adsorption module of BMS. A simulation box was constructed through
dynamic simulation using the COMPASS (Condensed-phase Optimized
Molecule Potential for Atomic Simulation Study) module. Only
surface-layer iron atoms were considered for the adsorption study. MD
simulation was carried out at room temperature using the NVT
ensemble, with a step time of 1 fs and a simulation period of 200 ps.
Physical adsorption parameters, such as interaction energy, Einteraction;
binding energy, Ebinding; and adsorption energy, Eads (each in kJ/mol),
were estimated using the adsorption module of BMS software. Fig. 13
depicts the results of the adsorption study performed on the Fe (110)
surface. The interaction energy between MS and AI was estimated ac­
cording to Eq. (19).
(
EInt = ETotal − ESurface+H2 O + H3 O+ +Cl− + EInhibitor
)
(19)
2.7.1. Biochemical assay of waste acid after weight loss study
The wastewater after weight-loss experiments was tested for its
biochemical oxygen demand (BOD) and chemical oxygen demand
(COD) by the standard test procedure recommended by the Central
Pollution Control Board (CPCB), Government of India, New Delhi, to
assess the biodegradability of AI as a GI [48,49].
3. Results and discussion
Fig. 1 (A, B) depicts the theoretical and experimental FTIR spectra of
the flavonoid. The vibrational mode assignment and potential energy
distribution (PED) of the flavonoid molecule can be summarized as
follows. The broad peak in the range 3400–3500 cm− 1 can be ascribed to
O–H groups. The broad peak in the range 1500–1600 cm− 1 can be
attributed to aromatic rings. The multiplet in the range 1010–1050 cm− 1
can be ascribed to a saturated alcohol group. A low-intensity symmetric
stretching vibration due to O–H is also evident at 3621 cm− 1. A peak at
1620 cm− 1 can be ascribed to symmetric stretching vibration of a C– –C
− 1
bond of an aromatic ring. The strong peak at 1735 cm can be ascribed
to a C–– O stretching vibration. The two peaks at 2850 and 2890 cm− 1
can be ascribed to C–H stretching (symmetric and asymmetric)
8
Journal of Physics and Chemistry of Solids 165 (2022) 110690
vibrations of an aromatic ring [50].
Fig. 2 shows the 1H NMR spectrum of the flavonoid molecule, which
features a signal at δ = 7.26 ppm due to aromatic protons, and signals at
δ = 1.25 and 1.55 ppm due to aliphatic CH2 protons, which may be due
to some hydrocarbon contaminants. The signal at δ = 0.0 ppm is due to
tetramethylsilane used as a reference. Both FTIR spectroscopy and NMR
spectrometry supported the presence of flavonoid molecules as major
constituents of the leaf extract of AI [23–25].
3.1. Gravimetric experiments
Gravimetry is an established method for selecting the concentration
and nature of corrosive medium, time and temperature of exposure of
MS to corrosive medium so that one can plan his or her corrosion ex­
periments. Table 1 shows the weight change (mg), deviation (absolute
and standard), precision, CR, and CIE of MS at different concentrations
of AI extract at 298 K. Fig. 3 depicts the change in CIE with respect to AI
concentration. Each gravimetric experiment was performed in triplicate
to ensure the precision of the results. Average weight losses are listed in
Table 1. The CR was found to decrease with increasing concentration of
AI extract [51]. The CIE increased with increasing AI extract concen­
tration from 0.1 to 4 g/L. AI gave 89.25% CIE at 4.0 g/L, which proved
to be the optimum concentration. This result compares favorably with
previously reported data. The acid extracts of E. crassipes were reported
to show 70% CIE for MS at 4 g/L and 30 ◦ C in 5.0 M HCl [2]. M. Koenigii
leaves were reported to show 96% CIE for MS in 1.0 M hydrochloric acid
at 600 ppm and 308 K [5]. Henna leaf extract (1.2 g/L) was reported to
show 92% CIE for MS in 1.0 M HCl solution [8]. In the present study, AI
has been found to confer good CIE at a low concentration, i.e., 50% at
0.1 g/L at 298 K. The increase in CIE with increasing concentration of AI
extract can be attributed to the increase in barrier film thickness and
hence a decrease in the rate of dissolution of the metal in HCl [52,53].
3.2. Polarization study
The polarization of an MS electrode was studied to determine the
structure, behavior, and kinetics of double-layer formation at the MS/
HCl interface. The values of icorr, corrosion potential (Ecorr), cathodic and
anodic Tafel slopes, CR, OCP, and CIE are listed in Table 2. Fig. 4 shows
the change in OCP with time, and the corresponding Tafel plots are
shown in Fig. 5. A change in OCP from − 528 to − 686 mV implies a
mixed type of inhibition. The nature and slope of the anodic and
cathodic polarization curves remain almost the same in the blank solu­
tion and in the presence of different concentrations of AI (Fig. 5). This
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

Fig. 13. Equilibrium adsorption configurations of Flavonoids molecule on Fe (1 1 0) surface obtained by MD simulations. (A): top view, (B and C): side view before
starting adsorption simulation study, (D and E): side view, (F): top view after adsorption simulation study. Only top layer of Fe atoms (highlighted) was selected for
adsorption of Flavonoid molecule.

Table 1
Weight loss, corrosion rate and corrosion inhibition efficiency (CIE) of Azardirachta indica (AI) at different concentrations by Gravimetric technique at 25 ◦ C in 5 M HCl.
Concentration (g/l) Average weight loss, (mg) Absolute deviation Standard deviation (σd) Precision in weight measurement (mg) Corrosion rate (mpy) CIE (%)

Blank 50.75 0.05 0.02 50.75 ± 0.02 664.231 –

0.1 25.1 0.03 0.01 25.1 ± 0.01 327.8949 50.64
0.5 12.9 0.04 0.02 12.9 ± 0.02 168.4952 74.63
1 10.8 0.03 0.02 10.8 ± 0.02 141.2088 78.74
2 9.02 0.02 0.01 9.02 ± 0.01 117.9793 82.23
4 5.45 0.02 0.01 5.45 ± 0.01 71.3896 89.25

indicates that the chemical nature of the interface does not change with
the addition of AI, highlighting the mildness of this GI. The addition of
AI to HCl increases ECorr. and decreases iCorr. , presumably due to an in­
crease in the rate of adsorption with increasing concentration of AI
extract [54]. No passive region was observed in the anodic polarization
curves, even on shifting the polarization potential from the OCP to 550
mV, indicating that no oxide film was developed on the MS surface [55].
Increasing coating thickness with increasing concentration of AI extract
was also indicated by metallurgical imaging. Increases in resistance
polarization (Rp) and thickness of the barrier film were observed with
increasing concentration of AI extract [56]. Specifically, Rp increased
from 53.6 to 562.6 Ω/cm2. A maximum CIE of 79.46% was observed in
the polarization study.

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H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

Table 2
Open Circuit Potential (OCP), corrosion current density (Icorr), anodic Tafel slope (βa), cathodic Tafel slope (βc), Resistance polarization (Rp), corrosion rate (CR) and
CIE of Azardirachta indica at different concentrations for mild steel by electrochemical polarization method at 25 ◦ C in 5 M HCl.
Concentration (g/l) OCP (− mV versus Ag/AgCl Icorr (μA/cm2) βa (mV/dec) − βc (mV/dec) Rp (Ω/cm2) CR (mpy) CIE

Blank 528 14.48 5.935 7.637 53.6 1.7279 –

0.1 608 12.27 7.811 8.828 125.3 0.8755 49.33
0.5 623 12.01 15.493 9.990 138.2 0.7752 55.13
1 647 9.78 18.164 11.659 153.8 0.6865 60.26
2 658 5.10 21.215 13.501 465.3 0.4242 75.44
4 686 2.92 22.286 14.549 562.6 0.3548 79.46

concentration. The CIE increased with increasing AI extract concentra­

Table 3 tion with a concomitant increase in the degree of surface coverage (θ)
Amount of gas evolved (ml), degree of surface covered (θ) and corrosion inhi­ from 48% to 86%.
bition efficiency (CIE) in presence of Azardirachta indica (AI) as environment
friendly corrosion inhibitor at different concentrations by Gasometric technique
3.4. Impedance study
at 25 ◦ C in 5 M HCl as corroding solution.
Concentration (g/l) RVh Surface coverage (θ) CIE The impedance method was used to probe the MS/AI interface and to
Blank 1.0787 – – characterize the adsorption and corrosion inhibition mechanism oper­
0.1 0.3363 0.4882 48.82 ative on the surface of MS after the addition of AI extract. Impedance
0.5 0.2681 0.6515 65.15 study provides a fast and reliable method for assessing the performance
1 0.2146 0.7010 70.10
2 0.2146 0.8010 80.10
of any corrosion inhibitor at an MS/inhibitor interface [57–59]. The
4 0.2106 0.8647 86.47 advantage of impedance spectroscopy is that it can be used to measure
the corrosion behavior of any inhibitor in a corrosive medium with
respect to time and frequency [60]. To support the electrochemical
polarization experiments and to understand the formation and growth of
Table 4 the barrier film with increasing AI extract concentration, an impedance
Coating thickness (CT), percentage porosity (PP) and pore length (PL) of mild
study was performed (after attaining the OCP) over the wide frequency
steel samples with and without Azarichita indica (AI) as an environment friendly
range from 0.1 to 10 kHz. Fig. 6 displays the Nyquist plots for an MS
corrosion inhibitor.
working electrode immersed in 5.0 M hydrochloric acid containing
Concentration (g/ Coating Thickness Percentage Pore Length different concentrations of AI extract. The double-layer capacitance (Cdl )
l) (μm) porosity (μm)
was obtained according to Eq. (20) [61].
Blank 48.76 77.27 577.39
0.1 56.82 61.35 194.88 1
Cdl = (20)
0.5 140.34 48.37 157.86 2πfmax. RCT
1 185.23 36.51 142.23
2 215.91 24.66 113.70 The diameter of the semicircle increased with increasing AI extract
4 233.65 18.8 94.84 concentration, indicating an increase in charge-transfer resistance. The
capacitance Cdl is related to the concentration of charge carriers and the
dielectric constant of the medium in the interface region, both of which
Table 5 are related to the concentration of AI (flavonoid) in this region. The
Electrochemical impedance parameters for mild steel samples in 5 M HCl solu­ Nyquist plots exhibited compressed semicircles with only one capacitive
tion in absence and presence of different concentrations of Azadirachta indica loop, representing only one time constant. RCT and CIE increased,
(AI) at room temperature. whereas Cdl decreased, with increasing AI extract concentration
Concentration (g/ Cdl ( × 10− 5
F Rct (Ω Rs/Ω CIE % θ (Table 5). This behavior can be ascribed to a reduction in the dielectric
L) cm2) cm2) cm2 constant of the interface or an increase in the thickness of the electrified
Blank 8.9 50.76 1.11 – – interface, confirming the adsorption of AI molecules at the MS/AI
0.1 5.27 121.24 1.24 40.78 0.41 interface [62]. The CIE and degree of surface coverage increased with
0.5 4.13 135.32 3.32 53.59 0.53 increasing AI extract concentration. Fig. 7 shows the variation in
1 3.09 150.45 12.43 65.28 0.65
impedance with frequency (Bode curve) and the Randles equivalent
2 2.14 460.32 34.15 75.95 0.76
4 1.79 560.62 38.21 79.88 0.80 circuit model of the MS/AI interface. The individual Bode plots (original
scanned images) at different concentrations of AI are provided in the
ESI† (Fig. S1− S5). A Bode plot shows the variation of log(impedance)
3.3. Gasometric study versus log(frequency), and in the second Bode plot, phase shift is plotted
against log(frequency). A Bode plot yields information regarding the
The volume of gas released (mL), the fraction of surface coverage by resistance offered by an inhibitor film at low frequency, which can
AI (flavonoid), and CIE conferred by AI extract over the concentration sometimes be very difficult to measure from Nyquist plots. The equiv­
range 0–4 g/L at 25 ◦ C in 5 M HCl are listed in Table 3. The RVh decreased alent circuit contains a constant phase element (CPE), solution resis­
with increasing AI extract concentration over this range, which may tance (Rs), and charge-transfer resistance (Rct). The behavior of the Bode
have been due to a cathodic reaction [28–30]. The decrease in the plots shows that the MS/AI interface is under charge-transfer control, as
reduction process resulted in a decrease in CR with increasing AI extract confirmed by a single peak and the equivalent circuit model. The CPE

Table 6
Thermodynamic and kinetic parameters obtained from LAI and FAI study for leaf extract of AI (4.0 g/L) adsorbed on MS in 5 N HCl at 25 ◦ C.
Temperature ( C) Slope R2 Kads (L/mol) ΔG0ads (kJ/mol) ΔH0ads (kJ/mol) ΔS0ads (kJ/mol. K) Ea (kJ/mol)
◦

25 1.110 0.9913 123.46 − 26.29 − 23.012 0.011 27.4

10
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

decreased with increasing AI extract concentration, confirming the

Abbreviations; ΔE: Energy difference, I: Ionization energy, A: electron affinity, χ : Electrochemical potential, η: Global hardness, ΔN: Maximum charge transfer index, EAd : Adsorption energy, ω: electrophilicity, ω+:
DFT simulation chemical reactivity parameters for Flavonoid molecule (C15H10O7) for MS in 5 M HCl at room temperature obtained from Gaussian09 software, Standard basis set used was B3LYP/6-31G(d) (6D, 7F).

− 0.115
formation of a uniform insulating film in the interface region of MS/AI.

(eV)
Rs and Rct increased with increasing concentration of AI extract in the

PA
medium, as befits increasing thickness of the insulating film [60].

correction to
G (Hartree/
ΔΨ (− eV)
3.5. Metallurgical microscopy and SEM

Particle)
Thermal

0.1845
0.483
Metallurgical images obtained by MIT (blank and AI-treated) are
shown in Fig. 8. The MS surface became almost clear with increasing AI
extract concentration, due to decreases in the intensity and numbers of
correction to
Enthalpy, H
pits and cracks. Some evidence of uniform corrosion was seen on MS

(Hartree/
Particle)
Thermal

0.24913
ω− (au)

coupons in the presence of 0.1 g/L AI extract. The TC, PP, and LP in the
0.186

presence and absence of AI are shown in Table 4. The CT (μm) increased

from 56.82 to 233.65 μm and PP decreased from 61.35 to 18.8% on
correction to

increasing the AI extract concentration from 0.1 to 4.0 g/L. The metal­
E (Hartree/

lurgical microscopy results supported the impedance spectroscopy

Particle)
Thermal
ω+ (au)

0.2482
0.047

results.
To complement the metallurgical microscopy technique, SEM images
of corroded MS samples were acquired after gravimetric experiments.
energy (kCal/

Fig. 9 shows SEM images of blank and AI-treated MS surfaces. The

vibrational
Zero-point

surface topologies of the blank and AI-treated MS samples show uniform

144.557
ω (au)

2854

heterogeneous films composed of either AI molecules or corrosion

mol)

products formed during corrosion of MS in the HCl medium. The

electron accepting power, ω− : electron donating power, ΔΨ: metal inhibitor interaction energy, PA: proton affinity of the inhibitor molecule.

thickness of the film of corrosion products on the surface of MS

(Cal mol− 1
Entropy, S

decreased with increasing concentration of AI extract, confirming the

EAd (kJ/

135.947

formation of a uniform protective film of AI molecules on the surface of

mol)

K− 1 )
7.86

MS [63].
mol− 1 K− 1)

3.6. Adsorption and thermodynamic study

capacity,
ΔN (eV)

CV (Cal
0.0017

71.601
Heat

The surface coverage (θ) was obtained from Eq. (21) through
impedance study.
(Thermal)
Energy, E

kCal/mol

PCIE
σ (eV− 1)

(21)
155.741
Internal

θ=
0.563

100
Kads was obtained from Eq. (22).
mass (amu)

CIn 1
Molecular

= + CInh (22)
302.042

θ Kads
η (eV)

1.755

Fig. 10 shows the LAI and FAI of the blank and AI-treated samples.
Table 6 shows LAI parameters for the adsorption of AI extract on the MS
surface. The regression coefficient (R2) indicates near linearity, i.e.,
Symmetry

4.662 ×

0.997 [64]. ΔG ads was calculated from Kads according to Eq. (23).
◦
χ (eV)

3.951

KE of

101
A′′

ΔG0Ads = − RTln(55.5 × Kads ) (23)

Kads was obtained according to Eq. (24).

Symmetry

1.047 ×
− 2.364
A (eV)

KE of

ΔG0
1 −
103

(24)
ads
Kads = e
A′

RT
55.5
The van ’t Hoff relationship was used to determine ΔH0ads, and
moment (xy
Quadrupole

− 134.3630

ΔS0ads was calculated from Eq. (25).

− 5.423
I (eV)

(25)
axis)

ΔG0ads = ΔH0ads − TΔS0ads

The Ea was obtained from Eq. (26).

moment
ΔE (eV)

− 3.059

1.3755
Dipole

Ea
log CR = logA − (26)
(D)

2.303 RT
The adsorption of AI extract results in an increase in ΔS0ads. A sig­
nificant ΔG*ads of − 26.29 kJ/mol and a low value of Ea show that
Rotational
constants

0.55774

adsorption is thermodynamically controlled at room temperature.

(− eV)

(GHz)
ELUMO

2.364

Hence, adsorption of AI on MS is spontaneous, and obeyance of the

Langmuir isotherm proves chemical adsorption.
Repulsive
energy

3.7. Computational study

Nuclear

1.7179
Table 7

EHUMO
(− eV)

5.423

(D)

Various computational approaches, namely DFT, MD simulation,

11
H. Kumar et al. Journal of Physics and Chemistry of Solids 165 (2022) 110690

Table 8
Fukui nucleophilic, electrophilic, and radical attack parameters of Flavonoid for the top layers of Fe (110) surface of mild steel.
Electrophilic Attack (− ) Nucleophilic Attack (+) Radical Attack (0)

Atom Mulliken Hirshfeld Mulliken Hirshfeld Mulliken Hirshfeld

C (1) 0.028 0.042 0.029 0.043 0.028 0.043

C (2) 0.049 0.069 0.023 0.022 0.036 0.045
C (3) 0.044 0.037 0.007 0.012 0.026 0.025
C (4) 0.026 0.027 0.006 0.009 0.016 0.018
C (5) 0.032 0.052 0.020 0.024 0.026 0.038
C (6) 0.051 0.067 0.022 0.035 0.037 0.051
O (7 0.026 0.029 0.035 0.038 0.031 0.034
C (8) 0.006 0.011 0.046 0.057 0.026 0.034
C (9) 0.035 0.038 0.026 0.041 0.031 0.040
H (10) 0.040 0.022 0.043 0.023 0.041 0.022
O (11) 0.108 0.104 0.039 0.040 0.074 0.072
H (12) 0.032 0.032 0.025 0.019 0.029 0.026
O (13) 0.079 0.080 0.016 0.020 0.048 0.050
H (14) 0.044 0.040 0.025 0.020 0.035 0.030
C (15) − 0.000 0.000 0.001 0.018 − 0.001 0.009
C (16) 0.009 0.017 0.028 0.036 0.018 0.027
C (17) 0.016 0.022 0.021 0.034 0.018 0.028
C (18) 0.025 0.029 0.048 0.050 0.036 0.040
C (19) 0.016 0.018 0.021 0.027 0.018 0.022
C (20) 0.013 0.011 0.041 0.041 0.027 0.026
C (21) 0.013 0.025 0.067 0.069 0.040 0.047
H (22) 0.016 0.009 0.032 0.018 0.024 0.014
H (23) 0.031 0.017 0.046 0.025 0.038 0.021
H (24) 0.006 0.005 0.033 0.020 0.020 0.012
O (25) 0.022 0.022 0.033 0.032 0.027 0.027
H (26) 0.017 0.014 0.023 0.020 0.020 0.017
O (27) 0.027 0.029 0.038 0.042 0.033 0.036
H (28) 0.021 0.018 0.030 0.027 0.026 0.023
H (29) 0.058 0.031 0.045 0.026 0.052 0.029
H (30) 0.063 0.036 0.044 0.025 0.054 0.031
O (31) 0.047 0.045 0.088 0.086 0.068 0.065

frontier molecular orbital (FMO) analysis, and adsorption locator, were

Table 9 performed with Gaussian 09W and BMS. FMO study provides insight
Output obtained from MD simulation for adsorption of Flavonoid molecule on into electron distributions in the HOMO and LUMO, van der Waals
the top layer of Fe (1 1 0) surface of MS. surfaces, Electron Density Distribution (EDD) per atom, ionization en­
Systems Einteraction (kJ/ Ebinding (kJ/ Adsorption energy, EAds (kJ ergy, chemical potential, electron affinity, and so on. MD simulation
mol) mol) mol− 1) study provides insight into the structural arrangement of atoms and the
Fe- − 22.12 22.12 7.86 orientation of molecules on the MS, adsorption energies, equilibrium
Flavonoid adsorption configurations, interaction parameters, Fukui indices per
Note: H2O molecule used = 150 Nos, H3O+ = 15 Nos, Cl− = 15 Nos, Inhibitor =
atom, binding energies, and so on [65–67].
1, Surface plane was Fe (1 1 0), simulation box size = 39.56 × 39.56 × 75.63 Å,
Top layer of Fe atoms were used, Forcefield: COMPASS, and total simulation 3.7.1. FMO study
time is 200 ps? Fig. 11 shows the results of the computational study carried out on
the flavonoid molecule, and Fig. 12 depicts the electron clouds of its

Fig. 14. Mechanism of adsorption of Flavonoid on Fe (110) surface by physical and chemical mode.

12
H. Kumar et al.
Fig. 15. Biochemical Oxygen Demand (BOD) and Chemical Oxygen Demand (COD) of wastewater after weight loss experiments for Flavonoid molecule.
HOMO and LUMO. Table S1 (ESI†) lists the atomic coordinates and
Mulliken charges of the flavonoid adsorbed on an Fe (110) surface.
Table S2 (ESI†) lists the HOMOs and LUMOs, α-occupied eigenvalues,
and α-virtual eigenvalues. Table 7 lists theoretical data obtained from
DFT and BMS studies. The optical band gap between the HOMO and
LUMO was evaluated as 3.059 eV (Fig. 12). The greater the energy
residing in the HOMO, the greater the electron-donating ability of the
inhibitor [68]. Since the HOMO is higher in energy than the LUMO, the
flavonoid shows a strong tendency to coordinatively bond to the surface
layer of Fe atoms of MS. Back-donation of electrons takes place from
occupied d orbitals of Fe atoms to vacant sp2 hybridized orbitals of C
atoms i.e., C7, C11, and C15 (Fig. 12). The van der Waals surface per
atom is maximized on the terminal oxygen atoms (Fig. 11), whereas the
EDD is distributed uniformly over all of the atoms of the flavonoid
molecule.
3.7.2. Molecular dynamics simulation (MDS)
Fig. 13 shows the results of an adsorption locator study of the
flavonoid on an Fe (110) surface, and Table 8 lists the pertinent Fukui
functions. Fukui parameters were obtained by applying the constant
difference approximation in Hirshfeld population analysis using the
BMS software. Table 9 lists the adsorption parameters of the flavonoid
on an Fe (110) surface. A significant Einteraction of − 22.12 kJ/mol, and
high Ebinding and Eads of 22.12 kJ/mol and 7.86 kJ/mol, respectively,
support durable adsorption of the flavonoid on MS.
The negative MS-AI interaction energy (− 22.12 kJ/mol) confirms
robust chemisorption of AI extract (Table 9). The HOMO (nucleophilic)
and LUMO (electrophilic) active sites of AI flavonoid support the MDS
study of its adsorption and prove a very high degree of adsorption of its
molecules on the Fe (110) surface [64,65]. A low E, high S, and high
chemical potential, μ prove robust chemisorption of the AI (flavonoid)
(Table 7). High values of proton affinity, MS-AI interaction energy (ΔΨ ),
and EAd further confirm strong physisorption and appreciable CIE of AI
extract [69–72, 50]. MD simulation studies showed that the flavonoid
molecules occupy an almost flat linear position on the Fe (110) surface
along the first benzene ring of the inhibitor molecule (Fig. 13). This is
one of the main reasons for the high CIE shown by AI extract for MS in
5.0 M HCl.
3.8. Adsorption and inhibition mechanism of AI
Fig. 14 shows the probable adsorption mechanism of AI. Langmuir
and Frumkin isotherms, DFT, impedance, metallurgical imaging, and
SEM studies all indicated both physical and chemical adsorption of AI
extract. The AI extract forms an insulating film at its interface with MS,
the thickness of which increases with increasing AI extract
13
Journal of Physics and Chemistry of Solids 165 (2022) 110690
concentration, as manifested in increase in the diameter of the semi­
circle of the Nyquist loop, solution resistance, Rct, TC, PP, LP, vibrational
energy, thermal energy, and ΔG ads [73,74]. A strong coordinative bond
◦
is formed between the O of the AI flavonoid molecule and the Fe of MS,
which is instigated by the donation of e− from the flavonoid to vacant
d orbitals of Fe, followed by reverse donation of e− from d orbitals of Fe
to vacant π*-antibonding orbitals of the flavonoid [75–78]. This strong
bond between the flavonoid and MS was confirmed by significant
chemical potential, global softness, adsorption energy, and Fe/flavonoid
interaction energy [79,80].
3.9. Residual acid biochemical assay
As stipulated by the CPCB, the maximum permissible concentrations
of BOD and COD in water are 30 and 250 mg/L, respectively. Here, the
BOD and COD were estimated according to Eqs. (27) and (28).
BOD (mg/L) = dissolved oxygen of blank − dissolved oxygen of sample after
5 days. (27)
8 × 1000 × DFx Mx (VB − VS )
COD = (28)
Volume of sample taken
DF denotes dilution factor, Mx is molality (FeSO4), and VB and VS are
the volumes of (NH4)2Fe(SO4)2(H2O)6 solution consumed in blank and
sample titrations [81].
Fig. 15 shows the results of biochemical analysis of the residual acid
after gravimetric tests. The BOD/COD ratio provides insight into the
biodegradability. A high BOD/COD ratio represents high biodegrad­
ability. If the BOD/COD ratio of water lies in the range 0.24–0.36, then
water is said to be easily biodegradable [48, 49]. The BOD, COD, and
their ratio in the presence of AI were found to lie in the permissible
ranges stipulated by the CPCB of India.
4. Conclusions
The leaf extract of Azadirachta indica (AI) has been shown to be a
highly efficient inhibitor, anti-cracking, and anti-pitting agent for mild
steel (MS) in 5.0 M HCl. The adsorption and inhibition mechanism of AI
(flavonoid) on MS has been extensively investigated by experimental
and computational techniques. The inhibition efficiency follows a linear
relationship with the concentration of the AI extract, and conforms to
the Langmuir adsorption isotherm. Polarization of an MS electrode has
shown that AI extract affects both anodic and cathodic reactions and
thus has mixed control. Impedance measurements have revealed that Rct
and Rs increase with increasing inhibitor concentration, indicating that
the extent of adsorption increases with the concentration of the AI
extract. Surface studies have confirmed an increase in adsorption with
H. Kumar et al.
increasing inhibitor concentration. Metallurgical microscopy has
revealed that the thickness of the coating increases and that PP decreases
with increasing AI extract concentration. SEM, metallurgical micro­
scopy, LAI/FAI (ΔGads. < − 28.47 kJ/mol), and DFT studies have
◦
confirmed the formation of a barrier film on MS. A negative
MS− inhibitor Einteraction (− 22.12 kJ/mol), proton affinity, HOMO/
LUMO energies, electron distribution, van der Waals surfaces, and a high
EAd (7.86 kJ/mol) all prove strong adsorption of flavonoid molecule on
the surface of MS. The flavonoid molecule of AI adsorbs in an almost flat
and parallel orientation on the MS surface. A maximum of 89.25% in­
hibition efficiency was shown by AI extract on MS at 4.0 g/L (optimum
concentration) in 5.0 M HCl. Biochemical assay of AI-treated waste acid
showed its composition to lie within permissible limits stipulated by the
Pollution Board of the Government of India.
Authorship contributions
Conception and Design of Study: Harish Kumar, Vikas Yadav.
Acquisition of Data: Harish Kumar, Vikas Yadav.
Analysis and/or Interpretation of Data: Harish Kumar, Vikas
Yadav, and Anu Kumari.
Drafting the Manuscript: Harish Kumar.
Revising the Manuscript Critically for Important Intellectual Con­
tent: Harish Kumar.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors duly acknowledge the authorities at CDLU, Sirsa, for
providing infrastructural support for this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpcs.2022.110690.
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